WO2011152498A1 - Water-and-oil repellent agent, and water-and-oil repellent agent composition - Google Patents

Water-and-oil repellent agent, and water-and-oil repellent agent composition Download PDF

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Publication number
WO2011152498A1
WO2011152498A1 PCT/JP2011/062730 JP2011062730W WO2011152498A1 WO 2011152498 A1 WO2011152498 A1 WO 2011152498A1 JP 2011062730 W JP2011062730 W JP 2011062730W WO 2011152498 A1 WO2011152498 A1 WO 2011152498A1
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Prior art keywords
water
oil repellent
compound
group
fluorine
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PCT/JP2011/062730
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French (fr)
Japanese (ja)
Inventor
星野　泰輝
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旭硝子株式会社
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Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to EP11789900.5A priority Critical patent/EP2578659B1/en
Priority to CN201180027016.6A priority patent/CN102918131B/en
Priority to JP2012518453A priority patent/JP5846118B2/en
Publication of WO2011152498A1 publication Critical patent/WO2011152498A1/en
Priority to US13/693,654 priority patent/US8754183B2/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/84—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/42—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to a water / oil repellent and a water / oil repellent composition.
  • Patent Document 1 or 2 as a fluorine-containing urethane compound having a polyfluoroalkyl group, a reaction product of polyisocyanate and a fluorine-containing alcohol having 8 or more carbon atoms in the polyfluoroalkyl group (including other alcohols). Fluorine-containing urethane compounds that have been used have been used.
  • EPA US Environmental Protection Agency
  • a compound having a perfluoroalkyl group having 8 or more carbon atoms may be decomposed in the environment or in the living body, and the decomposition product may accumulate, that is, the environment. It is pointed out that the load is high. Therefore, a water / oil repellent composition having a polyfluoroalkyl group having 6 or less carbon atoms is required.
  • Patent Document 3 describes a fluorine-containing urethane compound which is a reaction product of a fluorine-containing alcohol having a C4 perfluoroalkyl group and a sulfonyl group and a polyisocyanate in order to reduce environmental burden.
  • articles treated with the water / oil repellent composition comprising the reaction product have not been sufficient in water / oil repellent performance.
  • Patent Document 4 describes a urethane compound obtained by reacting a perfluoroalkyl group having 4 or less carbon atoms and a fluorine-containing acrylic oligomer having a hydroxyl group at its terminal with polyisocyanate.
  • a urethane compound obtained by reacting a perfluoroalkyl group having 4 or less carbon atoms and a fluorine-containing acrylic oligomer having a hydroxyl group at its terminal with polyisocyanate.
  • two steps of a step of obtaining an oligomer having a functional group capable of reacting with isocyanate by polymerization and a step of reacting the oligomer with isocyanate are necessary, and the production process becomes complicated.
  • JP 58-189284 A Japanese Patent Laid-Open No. 62-181385 International Publication No. 2006/013791 International Publication No. 2007/002894
  • a water / oil repellent comprising a reaction product of the following fluorine-containing compound (a) and a polyisocyanate compound (b).
  • R f is a polyfluoroalkyl group having 1 to 6 carbon atoms
  • X is a single bond, an alkylene group having 1 to 4 carbon atoms
  • (CH 2 ) p OCO p is an integer of 1 to 4
  • Ph is a phenylene group
  • Y is a single bond, an alkylene group having 1 to 4 carbon atoms, or (CH 2 ) q O (CH 2 ) r (q is an integer of 0 to 4, r is an integer of 1 to 4), and Z is OH or
  • the water / oil repellent of the present invention does not contain a perfluoroalkyl group having 8 or more carbon atoms, it does not generate perfluorooctanoic acid (PFOA), is safe and has a low environmental impact, and has sufficient repellency on the surface of the article.
  • PFOA perfluorooctanoic acid
  • Water and oil repellency can be imparted.
  • the water / oil repellent composition of the present invention can impart sufficient water / oil repellency to the surface of an article and has a low environmental load.
  • the water / oil repellent of the present invention comprises a reaction product of a fluorine-containing compound (a), a polyisocyanate compound (b), and, if necessary, a compound (c).
  • the fluorine-containing compound (a) in the present invention is a fluorine-containing alcohol or a fluorine-containing amine having a phenylene group represented by the following formula (I), and two or more of them can also be used.
  • R f X—Ph—YZ
  • X is a polyfluoroalkyl group having 1 to 6 carbon atoms
  • X is a single bond, an alkylene group having 1 to 4 carbon atoms, (CH 2 ) m O (CH 2 ) n (m and n are independent of each other) Or an integer of 0 to 4), or (CH 2 ) p OCO (p is an integer of 1 to 4)
  • Ph is a phenylene group
  • Y is a single bond, an alkylene group having 1 to 4 carbon atoms, or (CH 2 ) q O (CH 2 ) r (q is an integer from 0 to 4, r is an integer from 1 to 4)
  • Z is OH or NHR (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) ).
  • the polyfluoroalkyl group is an alkyl group in which a majority of hydrogen atoms are substituted with fluorine atoms.
  • R f is preferably a perfluoroalkyl group in which all hydrogen atoms bonded to carbon are converted to fluorine atoms, and more preferably a linear perfluoroalkyl group having 4 to 6 carbon atoms.
  • X is a single bond, an alkylene group having 1 to 4 carbon atoms, (CH 2 ) m O (CH 2 ) n (m and n are each independently an integer of 0 to 4), or ( CH 2 ) p OCO (p is an integer of 1 to 4).
  • Ph represents a phenylene group.
  • it may be any of 1,2-phenylene group, 1,3-phenylene group and 1,4-phenylene group, and the hydrogen atom of phenylene group may be substituted with a substituent.
  • a substituent A low reactive thing is preferable from a synthetic viewpoint, and an alkyl group, an alkoxy group, an acyl group, a cyano group, a nitro group etc. can be illustrated. In the present invention, it is preferable from the viewpoint of availability of raw materials that Ph is a 1,4-phenylene group.
  • Y is a single bond, an alkylene group having 1 to 4 carbon atoms, or (CH 2 ) q O (CH 2 ) r (q is an integer of 0 to 4, r is an integer of 1 to 4) Indicates.
  • Z represents OH or NHR (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
  • the fluorine-containing compounds (a) represented by the above formula (I) in particular, the compounds represented by the following formula (a1) or (a2) impart water and oil repellency to the article surface. It is preferable because it is possible.
  • the water / oil repellent of the present invention reacts with the polyisocyanate compound (b) to become a fluorine-containing urethane compound, and if it is a fluorine-containing amine, the polyisocyanate compound. It becomes a fluorine-containing urea compound by reacting with (b).
  • the method for producing the fluorine-containing compound (a) in the present invention is not particularly limited. For example, it can be manufactured by the following manufacturing method.
  • a compound represented by the general formula: X 1 OCOPhZ 1 (wherein X 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z 1 represents a hydroxyl group or an amino group) is used as a starting material, As shown in the following reaction formula, a compound having an R F group is reacted to obtain compound (a1) or (a2).
  • an acid such as 4-toluenesulfonic acid monohydrate, sulfuric acid, or a base such as potassium carbonate or triethylamine as a catalyst.
  • the reaction is carried out without solvent or in a solvent, and among them, toluene, 2-butanone and the like can be used.
  • the ratio of the catalyst and the solvent is preferably 0.01 to 10 parts by mass of the catalyst and 0 to 5000 parts by mass of the solvent with respect to 100 parts by mass of the total amount of the above starting material and C 6 F 13 C 2 H 4 OH.
  • the reaction conditions are: reaction vessel: glass, SUS, etc., temperature: 50 to 150 ° C., pressure: ⁇ 0.1 to 1 MPa, atmosphere: gas replacement with nitrogen, argon, etc., time: 1 to 100 hours, etc. Conditions are mentioned. Furthermore, it is preferable to carry out the reaction while distilling off reaction by-products as necessary.
  • the compound (a1) or (a2) may be purified from the reaction crude liquid obtained by the above reaction.
  • a purification method for example, excess raw material components are distilled off from the reaction crude liquid, methanol, chloroform or the like is added thereto, and the compound (a1) or (a2) is recrystallized. Examples include a method of distilling off the raw material components, adding dichloropentafluoropropane, chloroform, ethyl acetate, and the like, washing several times with a sufficient amount of distilled water, and then distilling off the solvent.
  • the polyisocyanate compound (b) in the present invention is a compound having two or more isocyanate groups.
  • Examples of the polyisocyanate compound (b) include aliphatic, alicyclic and aromatic polyisocyanates having two or more isocyanate groups, mixtures of two or more of the polyisocyanates, and modifications obtained by modifying these. Polyisocyanate etc. are mentioned.
  • Examples of aliphatic, alicyclic and aromatic polyisocyanates having two or more isocyanate groups include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate (MDI). , Polymethylene polyphenyl polyisocyanate (common name: crude MDI or polymeric MDI), xylylene diisocyanate (XDI), and the like.
  • modified polyisocyanate examples include a prepolymer type modified product, a nurate modified product, a biuret modified product, a urethane modified product, a urea modified product, and a carbodiimide modified product of the polyisocyanate.
  • polyisocyanate compound (b) in the present invention hexamethylene diisocyanate or a modified product thereof is preferable from the viewpoint of the solubility of the obtained water / oil repellent.
  • the isocyanate group content in the polyisocyanate compound (b) is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and most preferably 15 to 30% by mass.
  • the reaction product in the present invention contains a reaction product of a compound (c) having an active hydrogen group reactive with an isocyanate group and a polyisocyanate compound (b). It may contain a reaction product of the polyisocyanate compound (b) with the fluorine-containing compound (a) and the compound (c) having an active hydrogen group reactive with an isocyanate group.
  • the active hydrogen group include a hydroxyl group, an amino group, a mercapto group, and the like.
  • the blocking agent which can block an isocyanate group may be sufficient.
  • water may be used. When an isocyanate group reacts with water, an amino group is generated by hydrolysis.
  • the generated amino group further reacts with another isocyanate to form a urea bond, and a crosslinked structure can be introduced into the molecule.
  • the reaction product in the present invention is a product obtained by reacting the compound (c) with respect to the isocyanate group of the polyisocyanate compound (b), preferably 0 to 50%, more preferably 0 to 30%.
  • the effect of the water / oil repellent of the present invention is substantially impaired (low environmental load and excellent water / oil repellency). Other properties can be imparted.
  • Two or more kinds of compounds (c) may be used.
  • the compound (c) in the present invention includes a compound having one active hydrogen group as an alcohol having a polyfluoroalkyl group, a linear or branched alkyl alcohol, an alcohol having a functional group other than a hydroxyl group, alcohol-modified silicone, polyoxy Examples include alcohols having an alkylene chain. Further, it may be a compound having a plurality of active hydrogen groups (polyhydric alcohol) or a blocking agent. Among them, the compound (c) is preferably a compound having one active hydrogen group because the solubility of the water / oil repellent in a solvent can be improved.
  • Examples of the compound having one amino group as an active hydrogen group include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, dodecylamine, cetylamine, stearylamine, behenylamine, diethylamine and dibutylamine.
  • polyhydric alcohols examples include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and triethylene glycol. , Tetraethylene glycol, polyethylene glycol, dipropylene glycol, glycerin, pentaerythritol, dipentaerythritol, monosaccharide, disaccharide, oligosaccharide and the like.
  • Examples of the compound containing an amino group include ethylenediamine, propylenediamine, and hexamethylenediamine.
  • the blocking agent examples include 3,5-dimethylpyrazole, acetoxime, methyl ethyl ketoxime, benzophenone oxime, thiophenol, hydroxylamine, primary amino mercaptan, secondary amino mercaptan, and the like. Particularly preferred is methyl ethyl ketoxime or 3,5-dimethylpyrazole.
  • Compound (c) may be used alone or in combination of two or more.
  • the reaction product in the present invention can be obtained by reacting the fluorine-containing compound (a) with the polyisocyanate compound (b).
  • the compound (c) other than the fluorine-containing compound (a) is also reacted, the fluorine-containing compound (a) and the compound (c) are sequentially reacted with the polyisocyanate compound (b), or the fluorine-containing compound (a) and the compound are reacted.
  • a catalyst and a reaction solvent can be appropriately used.
  • reaction product when Z of the fluorine-containing compound (a) is an amino group (NH 2 ), depending on the reaction conditions, the reaction product further reacted with a hydrogen atom of a urethane bond or urea bond as a product. You may include things.
  • the proportions of the fluorine-containing compound (a) and the polyisocyanate compound (b) are the active hydrogen groups (hydroxyl group, amino group, mercapto group, etc.) of the fluorine-containing compound (a) and the polyisocyanate compound (b). It is preferable to adjust the number of moles of the isocyanate group to be 1: 1. When the compound (c) is also reacted, the total number of active hydrogen groups of the fluorine-containing compound (a) and the compound (c) and the number of moles of isocyanate groups in the polyisocyanate compound (b) are 1: 1. It is preferable to adjust to.
  • the fluorine-containing compound (a) and the reaction product of the compound (c) and the polyisocyanate compound (b) may contain the unreacted fluorine-containing compound (a) and the compound (c). Although a part of the isocyanate group of b) may be unreacted, it is preferable that 80% or more of the fluorine-containing compound (a) and the compound (c) are reacted with the isocyanate group based on the total amount thereof. 80% or more of the isocyanate groups of the polyisocyanate compound (b) are preferably reacted.
  • the reaction product When producing a reaction product having no isocyanate group, the reaction product is produced by adjusting the ratio of the active hydrogen group and the isocyanate group as described above, as well as detecting the isocyanate group of the produced reaction product.
  • the isocyanate group of the reaction product is preferably 5% or less, more preferably substantially zero.
  • the desired reaction product can be produced using a method in which compound (c) or the like is added and the reaction is continued until no isocyanate group is detected.
  • a tertiary amine triethylamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine, etc.
  • carboxylic acid metal salt Potassium acetate, potassium 2-ethylhexanoate, etc.
  • organometallic compounds dibutyltin dilaurate, etc.
  • the amount of the catalyst is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the raw material mixture (the total of the fluorine-containing compound (a), the polyisocyanate compound (b) and the compound (c)).
  • the reaction solvent is not particularly limited as long as it does not have an active hydrogen group capable of reacting with an isocyanate group, and halogen compounds, hydrocarbons, ketones, esters, ethers, nitrogen compounds, sulfur and the like are used.
  • halogen compound examples include halogenated hydrocarbons and halogenated ethers.
  • halogenated hydrocarbon examples include hydrochlorofluorocarbon, hydrofluorocarbon, chlorinated hydrocarbon and the like.
  • hydrofluorocarbon examples include CF 3 CHFCHFCF 2 CF 3 , CF 3 (CF 2 ) 4 CHF 2 , CF 3 CF 2 CF 2 CH 2 CH 2 CH 3 , CF 3 (CF 2 ) 5 CH 2 CH 3 , 1,1 2,2,3,3,4-heptafluorocyclopentane and the like.
  • halogenated ether examples include hydrofluoroalkyl ether, hydrofluoro (alkyl alkenyl ether), hydrofluoro cyclic ether and the like.
  • hydrofluoroalkyl ethers include separated hydrofluoroalkyl ethers and non-separated hydrofluoroalkyl ethers.
  • the separate type hydrofluoroether is a compound in which one to R F group of etheric oxygen atom, an alkyl group at the other attached.
  • Non-separable hydrofluoroalkyl ether is a compound in which partially fluorinated alkyl groups are bonded to both sides of an etheric oxygen atom.
  • Examples of the separated hydrofluoroalkyl ether include CF 3 CF 2 CF 2 CF 2 OCH 3 , (CF 3 ) 2 CFCF 2 OCH 3 , CF 3 CF 2 CF 2 OCH 2 CH 3 , and (CF 3 ) 2 CFCF 2.
  • Examples of the non-separable hydrofluoroalkyl ether include CHF 2 CF 2 OCH 2 CF 3 and CF 3 CF 2 CH 2 OCF 2 CHF 2 .
  • Examples of the chlorinated hydrocarbon include methylene chloride, chloroform, 1,1,1-trichloroethane, dichloroethylene, trichloroethylene, and tetrachloroethylene.
  • hydrocarbons examples include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.
  • Aliphatic hydrocarbons include pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,4-trimethylpentane, 2,2 , 3-trimethylhexane, decane, undecane, dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, tetradecane, hexadecane and the like.
  • the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
  • aromatic hydrocarbons include benzene, toluene, xylene and the like.
  • ketone include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone (hereinafter referred to as MIBK), and the like.
  • ester examples include methyl acetate, ethyl acetate, butyl acetate, and methyl propionate.
  • ether examples include alkyl ethers such as methyl tert-butyl ether, diisopropyl ether and cyclopentyl methyl ether, and cyclic ethers such as dioxane and tetrahydrofuran.
  • Examples of the nitrogen compound include pyridine, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methylpyrrolidone and the like.
  • Examples of the sulfur compound include dimethyl sulfoxide and sulfolane.
  • chloroform, methyl ethyl ketone, MIBK, cyclohexanone, and DMF are particularly preferable from the viewpoint of solubility.
  • the reaction solvent one of the above may be used alone, or two or more may be used in combination.
  • the concentration of the raw material mixture in the reaction solvent is preferably 5 to 100% by mass, more preferably 10 to 90% by mass, and particularly preferably 20 to 80% by mass.
  • the reaction is preferably performed under anhydrous conditions in order to suppress side reactions.
  • the reaction temperature is 0 to 200 ° C., preferably 20 to 80 ° C.
  • the reaction time is preferably 1 to 200 hours.
  • the completion of the reaction can be confirmed by disappearance of a peak around 2280 cm ⁇ 1 derived from an isocyanate group by Fourier transform infrared spectrophotometer (FT-IR) measurement. For example, it can be confirmed by placing one drop of the reaction solution on a KBr window material and performing transmission type FT-IR measurement. Alternatively, the completion of the reaction can also be confirmed by taking a part of the reaction solution, removing the solvent by vacuum drying to obtain a reaction product solid, and performing reflection type FT-IR measurement.
  • the water / oil repellent of the present invention is preferably a reaction product having no isocyanate group (that is, no isocyanate group is detected by this measurement).
  • the water / oil repellent composition of the present invention is a composition comprising the water / oil repellent, a solvent, and optionally a surfactant and an additive.
  • the form of the water / oil repellent composition of the present invention is preferably a form in which the water / oil repellent is dissolved in a solvent or dispersed as fine particles.
  • the water / oil repellent composition of the present invention is produced by the following method (i), (ii), (iii) or (iv).
  • the solvent in the present invention include water, alcohol, glycol, glycol ether and the like in addition to the reaction solvent described above.
  • the water / oil repellent composition is a solution, a halogen compound, a ketone, or an ester is particularly preferred from the viewpoint of solubility and ease of handling.
  • the water / oil repellent composition is a dispersion, at least one medium composed of water, alcohol, glycol, glycol ether is particularly preferred in view of solubility and ease of handling.
  • Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, and 3-pentanol.
  • Examples include butanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, and 3-heptanol.
  • glycol and glycol ether ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol , Glycol ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol B propylene glycol monomethyl ether, polypropylene glycol, hexylene glycol, and the like.
  • the solid content concentration of the water / oil repellent in the reaction solvent is preferably 5 to 100% by weight in the solution (100% by weight), preferably 10 to 90% by weight, according to the preferred method for producing the water / oil repellent composition. Is more preferable, and 20 to 80% by mass is particularly preferable.
  • the solid content concentration is a concentration including a surfactant (emulsifier) in addition to the water / oil repellent.
  • the solid content concentration is calculated from the mass of the water / oil repellent composition before heating and the mass after drying in a convection dryer at 120 ° C. for 4 hours.
  • the water / oil repellent is used as the water / oil repellent composition.
  • a dilution component or the like may be appropriately added and adjusted.
  • the form of the water / oil repellent composition of the present invention is a dispersion
  • a water / oil repellent or a solution containing a water / oil repellent, a surfactant and an optional component are weighed, together with an appropriate amount of solvent, a homomixer, a high pressure
  • a usual method such as uniform stirring with an emulsifier or the like to form a dispersion is used.
  • the average particle size of the water / oil repellent in the dispersion type water / oil repellent composition is preferably 10 to 1000 nm, more preferably 10 to 300 nm, and particularly preferably 10 to 250 nm. If the average particle size is in this range, it is not necessary to use a large amount of a surfactant, etc., water repellency is good, no discoloration occurs when dyed fabrics are processed, and dispersion in the medium The particles can exist stably and do not settle.
  • the average particle diameter of the dispersion can be measured with a dynamic light scattering apparatus, an electron microscope, or the like, and the average particle diameter is a value measured with a dynamic light scattering apparatus.
  • conditions such as the type and amount of the surfactant, the rotation speed of the homomixer, and the pressure during high-pressure emulsification may be adjusted.
  • surfactant examples include a hydrocarbon-based surfactant and a fluorine-based surfactant, and an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant, respectively.
  • the surfactant from the viewpoint of dispersion stability, a combination of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant, or an anionic surfactant alone is preferable, and a nonionic surfactant is preferable. And a cationic surfactant are preferred.
  • the total amount of the surfactant is preferably 1 to 20 parts by mass and more preferably 1 to 15 parts by mass with respect to the water / oil repellent (100 parts by mass).
  • Additives include penetrants, antifoaming agents, water absorbing agents, antistatic agents, antistatic polymers, antifungal agents, texture modifiers, film-forming aids, water-soluble polymers (polyacrylamide, polyvinyl alcohol, etc.).
  • Thermosetting agent (melamine resin, urethane resin, triazine ring-containing compound, isocyanate compound, etc.), epoxy curing agent (isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, 1,6-hexa Methylene bis (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-para-phenylene) disemicarbazide, spiroglycol, etc.), thermosetting catalyst , Crosslinking catalysts, synthetic resins, fiber stabilizers, inorganic fine particles, and the like.
  • the amount of the additive is preferably 0 to 50% by mass and more preferably 0 to 20% by mass with respect to the water / oil repellent (100 parts by mass).
  • the water / oil repellent composition of the present invention may be a copolymer that exhibits water repellency and / or oil repellency other than the water / oil repellent of the present invention (for example, a commercially available water repellent, a commercially available water repellent, Oil repellent, commercially available water / oil repellent, etc.), water repellent compounds having no fluorine atom, and the like.
  • a commercially available water repellent a commercially available water repellent, Oil repellent, commercially available water / oil repellent, etc.
  • water repellent compounds having no fluorine atom include paraffinic compounds, aliphatic amide compounds, alkylethyleneurea compounds, silicone compounds, and the like.
  • the article that can be treated with the water / oil repellent composition of the present invention is not particularly limited, and various examples can be given.
  • it can be used for fibers (natural fibers, synthetic fibers, blended fibers, etc.), various fiber products, nonwoven fabrics, resins, paper, leather, metals, stones, concrete, gypsum, glass and the like.
  • Preferred applications include synthetic leather, carpets, curtains, wallpaper, vehicle interiors, and the like.
  • Examples of the treatment method include a method of applying or impregnating an article with a water / oil repellent composition by a known coating method and then drying. Furthermore, you may perform an antistatic process, a flexible process, an antibacterial process, a deodorizing process, a waterproof process, etc.
  • Examples of waterproofing include processing for providing a waterproof film.
  • Examples of the waterproof membrane include a porous membrane obtained from a urethane resin or an acrylic resin, a nonporous membrane obtained from a urethane resin or an acrylic resin, a polytetrafluoroethylene membrane, or a moisture-permeable waterproof membrane combining these.
  • the water / oil repellent of the present invention contains a reaction product obtained by reacting a fluorine-containing compound having a polyfluoroalkyl moiety having 6 or less carbon atoms as an alcohol with a polyisocyanate compound, and is treated with an article to treat the environment.
  • the load is small and sufficient water and oil repellency is imparted.
  • high quality water / oil repellency can be imparted to the article.
  • the obtained white solid was dissolved in 900 mL of ethyl acetate, transferred to a separatory funnel, washed twice with ion-exchanged water (1200 mL), and the solvent of the ethyl acetate layer was distilled off to remove 460.8 g of the following compound ( a1) (white solid) was obtained.
  • the yield was 98%.
  • the measurement result of 1 H-NMR of the obtained compound (a1) is shown below.
  • Each measured value means a measured value derived from the group shown in parentheses following the measured value. If there is a part surrounded by [] in this group, the measured value is surrounded by []. It means the measured value derived from the part.
  • the NMR measurement results shown in the examples are all the same.
  • the chemical shift (in CDCl 3 ) and the integrated intensity relative value derived from the aromatic ring of the compound (a1) are 6.9 ppm (integrated intensity relative value: 2) and 7.9 ppm (2).
  • the chemical shift and the integrated intensity relative value derived from the reactive organism that reacted with isocyanate and formed a urethane bond were 7.2 ppm (98) and 8.0 ppm (98), and the conversion rate was determined to be 98%.
  • Example 1 To a 100 mL glass reactor equipped with a stirrer, 2.77 g of Desmodur N-3200 (manufactured by Sumika Bayer Urethane Co., Ltd., modified HDI biuret, isocyanate group content: 22.7 mass%), compound (a1 ), 0.076 g of triethylamine as a catalyst, and 40.0 g of MIBK were added and stirred at room temperature for 48 hours to obtain a reaction solution containing a fluorine-containing urethane compound as a reaction product. The peak of the isocyanate group disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of compound (a1) by 1 H-NMR was 98%.
  • Example 2 To a 100 mL glass reactor equipped with a stirrer, 2.90 g of Duranate THA-100 (manufactured by Asahi Kasei Chemicals, modified HDI nurate, isocyanate group content: 21.2% by mass), 7 of compound (a1) .10 g, 0.074 g of triethylamine as a catalyst, and 40.0 g of MIBK were added and stirred at room temperature for 48 hours to obtain a reaction solution containing a fluorine-containing urethane compound as a reaction product. The isocyanate group peak almost disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of the compound (a1) by 1 H-NMR was 95%.
  • Example 3 To a 100 mL glass reactor equipped with a stirrer, 2.16 g of Cosmonate M-200 (manufactured by Mitsui Chemicals Polyurethanes, Polymeric MDI, isocyanate group content: 31.5 mass%), 7 of compound (a1) .84 g, 0.082 g of triethylamine as a catalyst, and 40.0 g of MIBK were added and stirred at room temperature for 100 hours to obtain a reaction solution containing a fluorine-containing urethane compound as a reaction product. The isocyanate group peak almost disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of the compound (a1) by 1 H-NMR was 90%.
  • Example 4 In a 100 mL glass reactor equipped with a stirrer, 1.52 g of TDI (manufactured by Tokyo Chemical Industry Co., Ltd., isocyanate group content: 48.3 mass%), 8.48 g of compound (a1), triethylamine as a catalyst 0.089 g and 40.0 g of MIBK were added and stirred at room temperature for 100 hours to obtain a reaction solution containing a fluorine-containing urethane compound as a reaction product. The isocyanate group peak almost disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of compound (a1) by 1 H-NMR was 92%.
  • Example 5 A 100 mL glass reactor equipped with a stirrer was charged with 1.53 g of TDI, 8.47 g of compound (a2), and 40.0 g of MIBK, heated to 80 ° C., stirred for 100 hours, and reacted. A reaction solution containing a fluorine-containing urea compound as a product was obtained. The isocyanate group peak almost disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of compound (a2) by 1 H-NMR was 88%.
  • Example 6 In a 100 mL glass reactor equipped with a stirrer, 2.06 g of MDI (manufactured by Tokyo Chemical Industry Co., Ltd., isocyanate group content: 33.6% by mass), 7.94 g of compound (a2), and 40 of MIBK 0.0 g was added, and the mixture was heated to 80 ° C. and stirred for 100 hours to obtain a reaction solution containing a fluorine-containing urea compound as a reaction product. The isocyanate group peak almost disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of the compound (a2) by 1 H-NMR was 85%.
  • test plates were prepared by the following method to evaluate water and oil repellency.
  • a washed glass plate was used as a substrate, and the treatment liquid obtained above was applied thereon by spin coating for 10 seconds under the condition of 1000 rpm. Thereafter, a film was formed by heat treatment at 120 ° C. for 60 minutes to obtain a test plate. Using all of the above treatment solutions, a test plate formed with a film was prepared, and each test plate obtained was used to measure the contact angles of water and n-hexadecane on the coating. The water and oil repellency of the film obtained from the treatment liquid containing the water and oil repellent prepared in Examples and Comparative Examples was evaluated. The contact angle was measured using CA-X manufactured by Kyowa Interface Science Co., Ltd.
  • the contact angle value marked with * in the table is not an accurate value because the droplet on the film wets and spreads during the measurement, and it can be said that the water repellency is insufficient when the droplet spreads wet. .
  • the treatment liquid (water repellent composition) containing the water / oil repellent of the present invention contains the water / oil repellent of the comparative example which does not contain any of the components of the water / oil repellent of the present invention. It can be seen that a film having higher water / oil repellency can be produced than the treatment liquid (water / oil repellent composition). Moreover, if the processing liquid (water / oil repellent composition) containing the water / oil repellent of the present invention is used, sufficient water / oil repellency can be imparted to the article, and the environmental load is low.
  • test cloths were prepared by the following method to evaluate water repellency and oil repellency.
  • reaction solution was diluted with acetone (Examples 1 to 4 and Comparative Examples 1 to 2) or DMF (Examples 5 to 6) so that the solid content concentration was 0.6 g / L. did.
  • a polyester cloth was soaked in these test solutions, and the wet pick-up was squeezed to 100% by mass. This was dried at room temperature for 24 hours and further dried at 170 ° C. for 60 seconds to obtain a test cloth.
  • the water / oil repellent or water / oil repellent composition of the present invention is used for textile products (clothing articles (sportswear, coats, blousons, work clothes, uniforms, etc.), bags, carpets, curtains, wallpaper, and vehicle interiors. , Industrial materials, etc.), non-woven fabrics, leather products, stone materials, concrete building materials, and the like. Moreover, it is useful as a coating agent for filter materials and a surface protective agent. Furthermore, it is also useful for applications in which water and oil repellency is imparted by mixing and molding with fiber such as polypropylene, nylon and polyester. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2010-129002 filed on June 4, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Abstract

Provided is a water-and-oil repellent agent which can impart sufficient water-and-oil repellency to the surface of an article and which has a low environmental burden. Also provided is a water-and-oil repellent agent composition. Specifically disclosed is a water-and-oil repellent agent which contains a reaction product obtained by reacting a polyisocyanate compound with amine or a fluorine-containing alcohol comprising a polyfluoroalkyl moiety having 6 or less carbon atoms, has a low environmental burden, and imparts sufficient water-and-oil repellency to an article treated with said water-and-oil repellent agent. When the aforementioned article is treated with the abovementioned water-and-oil repellent agent composition, the article will be imparted with a high degree of water-and-oil repellency.

Description

撥水撥油剤および撥水撥油剤組成物Water / oil repellent and water / oil repellent composition
　本発明は、撥水撥油剤および撥水撥油剤組成物に関する。 The present invention relates to a water / oil repellent and a water / oil repellent composition.
　物品（繊維製品等。）の表面に撥水撥油性および防汚性を付与する方法としては、ポリフルオロアルキル基を有する種々の含フッ素化合物、特に含フッ素ウレタン化合物や含フッ素ポリマーを媒体に溶解させた溶液、または分散させたエマルションからなる撥水撥油剤組成物を用いて物品を処理する方法が知られている。 As a method for imparting water / oil repellency and antifouling properties to the surface of an article (textile product, etc.), various fluorine-containing compounds having a polyfluoroalkyl group, particularly fluorine-containing urethane compounds and fluorine-containing polymers are dissolved in a medium. There has been known a method for treating an article using a water / oil repellent composition comprising a dispersed solution or a dispersed emulsion.
　特許文献１または２には、ポリフルオロアルキル基を有する含フッ素ウレタン化合物として、ポリイソシアネートとポリフルオロアルキル基の炭素数が８以上の含フッ素アルコール（その他のアルコールも含む。）との反応生成物である含フッ素ウレタン化合物が用いられてきた。 In Patent Document 1 or 2, as a fluorine-containing urethane compound having a polyfluoroalkyl group, a reaction product of polyisocyanate and a fluorine-containing alcohol having 8 or more carbon atoms in the polyfluoroalkyl group (including other alcohols). Fluorine-containing urethane compounds that have been used have been used.
　しかし、最近、ＥＰＡ（米国環境保護庁）によって、炭素数が８以上のパーフルオロアルキル基を有する化合物は、環境、または生体中で分解し、分解生成物が蓄積するおそれがある点、すなわち環境負荷が高い点が指摘されている。そのため、炭素数が６以下のポリフルオロアルキル基を有する撥水撥油剤組成物が要求されている。 However, recently, according to EPA (US Environmental Protection Agency), a compound having a perfluoroalkyl group having 8 or more carbon atoms may be decomposed in the environment or in the living body, and the decomposition product may accumulate, that is, the environment. It is pointed out that the load is high. Therefore, a water / oil repellent composition having a polyfluoroalkyl group having 6 or less carbon atoms is required.
　特許文献３には、環境負荷を低減するため、炭素数４のパーフルオロアルキル基とスルホニル基を有する含フッ素アルコールとポリイソシアネートとの反応生成物である含フッ素ウレタン化合物が記載されている。しかし、上記反応生成物からなる撥水撥油剤組成物を用いて処理された物品は、撥水撥油性能が十分ではなかった。 Patent Document 3 describes a fluorine-containing urethane compound which is a reaction product of a fluorine-containing alcohol having a C4 perfluoroalkyl group and a sulfonyl group and a polyisocyanate in order to reduce environmental burden. However, articles treated with the water / oil repellent composition comprising the reaction product have not been sufficient in water / oil repellent performance.
　特許文献４には、炭素数が４以下のパーフルオロアルキル基とその末端に水酸基を有する含フッ素アクリルオリゴマーとポリイソシアネートを反応させたウレタン化合物が記載されている。ウレタン化合物を製造するには、重合によりイソシアネートと反応し得る官能基を末端に有するオリゴマーを得る工程と、オリゴマーをイソシアネートと反応させる工程の２段階が必要であり、製造工程が複雑になる。 Patent Document 4 describes a urethane compound obtained by reacting a perfluoroalkyl group having 4 or less carbon atoms and a fluorine-containing acrylic oligomer having a hydroxyl group at its terminal with polyisocyanate. In order to produce a urethane compound, two steps of a step of obtaining an oligomer having a functional group capable of reacting with isocyanate by polymerization and a step of reacting the oligomer with isocyanate are necessary, and the production process becomes complicated.
特開昭５８－１８９２８４号公報JP 58-189284 A 特開昭６２－１８１３８５号公報Japanese Patent Laid-Open No. 62-181385 国際公開第２００６／０１３７９１号International Publication No. 2006/013791 国際公開第２００７／００２８９４号International Publication No. 2007/002894
　本発明は、物品の表面に十分な撥水撥油性を付与でき、かつ環境負荷が低い撥水撥油剤、および撥水撥油剤組成物を提供することを目的とする。 It is an object of the present invention to provide a water / oil repellent and a water / oil repellent composition that can impart sufficient water / oil repellency to the surface of an article and have a low environmental load.
　本発明は、以下の撥水撥油剤、および撥水撥油剤組成物を提供する。
［１］下記含フッ素化合物（ａ）とポリイソシアネート化合物（ｂ）との反応生成物からなる撥水撥油剤。
  含フッ素化合物（ａ）：Ｒｆ－Ｘ－Ｐｈ－Ｙ－Ｚ
Ｒｆは炭素数１～６のポリフルオロアルキル基を、Ｘは単結合、炭素数１～４のアルキレン基、（ＣＨ２）ｍＯ（ＣＨ２）ｎ（ｍおよびｎは互いに独立して０～４の整数）、または（ＣＨ２）ｐＯＣＯ（ｐは１～４の整数）を、Ｐｈはフェニレン基を、Ｙは単結合、炭素数１～４のアルキレン基、または（ＣＨ２）ｑＯ（ＣＨ２）ｒ（ｑは０～４の整数、ｒは１～４の整数）を、ＺはＯＨまたはＮＨＲ（Ｒは水素原子または炭素数１～６のアルキル基）をそれぞれ表す。
［２］前記反応生成物が、イソシアネート基を有しない［１］に記載の撥水撥油剤。
［３］前記含フッ素化合物（ａ）のＲｆが炭素数４～６のパーフルオロアルキル基である、［１］または［２］に記載の撥水撥油剤。
［４］前記含フッ素化合物（ａ）が下式（ａ１）または（ａ２）で表される含フッ素化合物である、［１］～［３］に記載の撥水撥油剤。 The present invention provides the following water / oil repellent and water / oil repellent composition.
[1] A water / oil repellent comprising a reaction product of the following fluorine-containing compound (a) and a polyisocyanate compound (b).
Fluorine-containing compound (a): R f —X—Ph—YZ
R f is a polyfluoroalkyl group having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 4 carbon atoms, (CH 2 ) m O (CH 2 ) n (m and n are each independently 0 Or an integer of 1 to 4), or (CH 2 ) p OCO (p is an integer of 1 to 4), Ph is a phenylene group, Y is a single bond, an alkylene group having 1 to 4 carbon atoms, or (CH 2 ) q O (CH 2 ) r (q is an integer of 0 to 4, r is an integer of 1 to 4), and Z is OH or NHR (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
[2] The water / oil repellent according to [1], wherein the reaction product does not have an isocyanate group.
[3] The water / oil repellent according to [1] or [2], wherein R f of the fluorine-containing compound (a) is a perfluoroalkyl group having 4 to 6 carbon atoms.
[4] The water / oil repellent according to [1] to [3], wherein the fluorine-containing compound (a) is a fluorine-containing compound represented by the following formula (a1) or (a2).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
［５］前記ポリイソシアネート化合物（ｂ）が、ヘキサメチレンジイソシアネートまたはその変性体である、［１］～［４］のいずれかに記載の撥水撥油剤。
［６］［１］～［５］のいずれかに記載の撥水撥油剤と溶媒を含有する撥水撥油剤組成物。 [5] The water / oil repellent according to any one of [1] to [4], wherein the polyisocyanate compound (b) is hexamethylene diisocyanate or a modified product thereof.
[6] A water / oil repellent composition comprising the water / oil repellent according to any one of [1] to [5] and a solvent.
　本発明の撥水撥油剤は、炭素数８以上のパーフルオロアルキル基を含まないことから、パーフルオロオクタン酸（ＰＦＯＡ）の発生がなく安全で環境負荷が低く、かつ物品の表面に充分な撥水撥油性を付与できる。
  本発明の撥水撥油剤組成物は、物品の表面に充分な撥水撥油性を付与でき、かつ環境負荷が低い。 Since the water / oil repellent of the present invention does not contain a perfluoroalkyl group having 8 or more carbon atoms, it does not generate perfluorooctanoic acid (PFOA), is safe and has a low environmental impact, and has sufficient repellency on the surface of the article. Water and oil repellency can be imparted.
The water / oil repellent composition of the present invention can impart sufficient water / oil repellency to the surface of an article and has a low environmental load.
　本発明の撥水撥油剤は、含フッ素化合物（ａ）、ポリイソシアネート化合物（ｂ）、および必要に応じて化合物（ｃ）の反応生成物からなる。 The water / oil repellent of the present invention comprises a reaction product of a fluorine-containing compound (a), a polyisocyanate compound (b), and, if necessary, a compound (c).
　＜含フッ素化合物（ａ）＞
　本発明における含フッ素化合物（ａ）は、下式（Ｉ）で表されるフェニレン基を有する含フッ素アルコールまたは含フッ素アミンであり、それらの２種以上を使用することもできる。
Ｒｆ－Ｘ－Ｐｈ－Ｙ－Ｚ　・・・（Ｉ）
　ただし、Ｒｆは炭素数１～６のポリフルオロアルキル基であり、Ｘは単結合、炭素数１～４のアルキレン基、（ＣＨ２）ｍＯ（ＣＨ２）ｎ（ｍおよびｎは互いに独立して０～４の整数）、または（ＣＨ２）ｐＯＣＯ（ｐは１～４の整数）であり、Ｐｈはフェニレン基であり、Ｙは単結合、炭素数１～４のアルキレン基、または（ＣＨ２）ｑＯ（ＣＨ２）ｒ（ｑは０～４の整数、ｒは１～４の整数）であり、ＺはＯＨまたはＮＨＲ（Ｒは水素原子または炭素数１～６のアルキル基）である。 <Fluorine-containing compound (a)>
The fluorine-containing compound (a) in the present invention is a fluorine-containing alcohol or a fluorine-containing amine having a phenylene group represented by the following formula (I), and two or more of them can also be used.
R f —X—Ph—YZ (I)
Where R f is a polyfluoroalkyl group having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 4 carbon atoms, (CH 2 ) m O (CH 2 ) n (m and n are independent of each other) Or an integer of 0 to 4), or (CH 2 ) p OCO (p is an integer of 1 to 4), Ph is a phenylene group, Y is a single bond, an alkylene group having 1 to 4 carbon atoms, or (CH 2 ) q O (CH 2 ) r (q is an integer from 0 to 4, r is an integer from 1 to 4), Z is OH or NHR (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) ).
　ポリフルオロアルキル基は水素原子の過半数がフッ素原子に置換されたアルキル基である。Ｒｆは、炭素に結合する水素原子がすべてフッ素原子に変換されたパーフルオロアルキル基が好ましく、さらに炭素数４～６の直鎖状パーフルオロアルキル基が好ましい。 The polyfluoroalkyl group is an alkyl group in which a majority of hydrogen atoms are substituted with fluorine atoms. R f is preferably a perfluoroalkyl group in which all hydrogen atoms bonded to carbon are converted to fluorine atoms, and more preferably a linear perfluoroalkyl group having 4 to 6 carbon atoms.
　上記式（Ｉ）においてＸは、単結合、炭素数１～４のアルキレン基、（ＣＨ２）ｍＯ（ＣＨ２）ｎ（ｍおよびｎは互いに独立して０～４の整数）、または（ＣＨ２）ｐＯＣＯ（ｐは１～４の整数）を示す。 In the above formula (I), X is a single bond, an alkylene group having 1 to 4 carbon atoms, (CH 2 ) m O (CH 2 ) n (m and n are each independently an integer of 0 to 4), or ( CH 2 ) p OCO (p is an integer of 1 to 4).
　上記式（Ｉ）においてＰｈは、フェニレン基を示す。フェニレン基であれば、１，２－フェニレン基、１，３－フェニレン基および１，４－フェニレン基のいずれであってもよく、フェニレン基の水素原子が置換基で置換されていてもよい。置換基としては特に限定されないが、合成上の観点から反応性の低いものが好ましく、アルキル基、アルコキシ基、アシル基、シアノ基、ニトロ基等が例示できる。本発明においては、Ｐｈが１，４－フェニレン基であることが原材料の入手性の点で好ましい。 In the above formula (I), Ph represents a phenylene group. As long as it is a phenylene group, it may be any of 1,2-phenylene group, 1,3-phenylene group and 1,4-phenylene group, and the hydrogen atom of phenylene group may be substituted with a substituent. Although it does not specifically limit as a substituent, A low reactive thing is preferable from a synthetic viewpoint, and an alkyl group, an alkoxy group, an acyl group, a cyano group, a nitro group etc. can be illustrated. In the present invention, it is preferable from the viewpoint of availability of raw materials that Ph is a 1,4-phenylene group.
　上記式（Ｉ）においてＹは、単結合、炭素数１～４のアルキレン基、または（ＣＨ２）ｑＯ（ＣＨ２）ｒ（ｑは０～４の整数、ｒは１～４の整数）を示す。 In the above formula (I), Y is a single bond, an alkylene group having 1 to 4 carbon atoms, or (CH 2 ) q O (CH 2 ) r (q is an integer of 0 to 4, r is an integer of 1 to 4) Indicates.
　上記式（Ｉ）においてＺは、ＯＨまたはＮＨＲ（Ｒは水素原子または炭素数１～６のアルキル基）を示す。 In the above formula (I), Z represents OH or NHR (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
　本発明においては、上記式（Ｉ）で表される含フッ素化合物（ａ）のうちでも、特に、下式（ａ１）または（ａ２）で表される化合物が物品表面へ撥水撥油性を付与できることから好ましい。 In the present invention, among the fluorine-containing compounds (a) represented by the above formula (I), in particular, the compounds represented by the following formula (a1) or (a2) impart water and oil repellency to the article surface. It is preferable because it is possible.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　本発明の撥水撥油剤は、含フッ素化合物（ａ）が含フッ素アルコールであれば、ポリイソシアネート化合物（ｂ）と反応することで含フッ素ウレタン化合物となり、含フッ素アミンであれば、ポリイソシアネート化合物（ｂ）と反応することで含フッ素ウレア化合物となる。
  本発明における含フッ素化合物（ａ）の製造方法は、特に限定されるものではない。例えば、下記の製造方法によって製造することができる。 If the fluorine-containing compound (a) is a fluorine-containing alcohol, the water / oil repellent of the present invention reacts with the polyisocyanate compound (b) to become a fluorine-containing urethane compound, and if it is a fluorine-containing amine, the polyisocyanate compound. It becomes a fluorine-containing urea compound by reacting with (b).
The method for producing the fluorine-containing compound (a) in the present invention is not particularly limited. For example, it can be manufactured by the following manufacturing method.
　一般式：Ｘ１ＯＣＯＰｈＺ１（式中、Ｘ１は水素原子または炭素数１～４のアルキル基を、Ｚ１は水酸基またはアミノ基を表す。）で表される化合物を出発物質として用いて、以下の反応式に示すようにＲＦ基を有する化合物を反応させて化合物（ａ１）または（ａ２）を得る。
Ｘ１ＯＣＯＰｈＺ１　＋　Ｃ６Ｆ１３Ｃ２Ｈ４ＯＨ　→　Ｃ６Ｆ１３Ｃ２Ｈ４ＯＣＯＰｈＺ１
　上記反応においては、触媒として、４－トルエンスルホン酸１水和物、硫酸等の酸、または炭酸カリウム、トリエチルアミン等の塩基を用いることが好ましい。反応は、無溶媒、もしくは溶媒中で行われ、なかでも、トルエン、２－ブタノン等を用いることができる。 A compound represented by the general formula: X 1 OCOPhZ 1 (wherein X 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z 1 represents a hydroxyl group or an amino group) is used as a starting material, As shown in the following reaction formula, a compound having an R F group is reacted to obtain compound (a1) or (a2).
X 1 OCOPhZ 1 + C 6 F 13 C 2 H 4 OH → C 6 F 13 C 2 H 4 OCOPhZ 1
In the above reaction, it is preferable to use an acid such as 4-toluenesulfonic acid monohydrate, sulfuric acid, or a base such as potassium carbonate or triethylamine as a catalyst. The reaction is carried out without solvent or in a solvent, and among them, toluene, 2-butanone and the like can be used.
　触媒および溶媒の割合は、上記出発物質とＣ６Ｆ１３Ｃ２Ｈ４ＯＨの合計量１００質量部に対し、触媒を０．０１～１０質量部、溶媒を０～５０００質量部が好ましい。
  反応条件として好ましくは、反応容器：ガラス製、ＳＵＳ製等、温度：５０～１５０℃、圧力：－０．１～１ＭＰａ、雰囲気：窒素、アルゴン等によるガス置換、時間：１～１００時間等の条件が挙げられる。さらに必要に応じて反応副生成物を留去しながら反応を行うことが好ましい。 The ratio of the catalyst and the solvent is preferably 0.01 to 10 parts by mass of the catalyst and 0 to 5000 parts by mass of the solvent with respect to 100 parts by mass of the total amount of the above starting material and C 6 F 13 C 2 H 4 OH.
Preferably, the reaction conditions are: reaction vessel: glass, SUS, etc., temperature: 50 to 150 ° C., pressure: −0.1 to 1 MPa, atmosphere: gas replacement with nitrogen, argon, etc., time: 1 to 100 hours, etc. Conditions are mentioned. Furthermore, it is preferable to carry out the reaction while distilling off reaction by-products as necessary.
　さらに、上記反応によって得られた反応粗液から化合物（ａ１）または（ａ２）を精製してもよい。精製する方法としては、例えば、反応粗液から過剰の原料成分を留去し、これにメタノール、クロロホルム等を加え、化合物（ａ１）または（ａ２）を再結晶する方法、反応粗液から過剰の原料成分を留去し、ジクロロペンタフルオロプロパン、クロロホルム、酢酸エチル等を加え、十分な量の蒸留水で数回洗浄した後、溶媒を留去する方法等が挙げられる。 Further, the compound (a1) or (a2) may be purified from the reaction crude liquid obtained by the above reaction. As a purification method, for example, excess raw material components are distilled off from the reaction crude liquid, methanol, chloroform or the like is added thereto, and the compound (a1) or (a2) is recrystallized. Examples include a method of distilling off the raw material components, adding dichloropentafluoropropane, chloroform, ethyl acetate, and the like, washing several times with a sufficient amount of distilled water, and then distilling off the solvent.
　＜ポリイソシアネート化合物（ｂ）＞
　本発明におけるポリイソシアネート化合物（ｂ）とは、イソシアネート基を２つ以上有する化合物である。ポリイソシアネート化合物（ｂ）としては、イソシアネート基を２以上有する脂肪族系、脂環族系、芳香族系等のポリイソシアネート、該ポリイソシアネートの２種類以上の混合物、これらを変性して得られる変性ポリイソシアネート等が挙げられる。 <Polyisocyanate compound (b)>
The polyisocyanate compound (b) in the present invention is a compound having two or more isocyanate groups. Examples of the polyisocyanate compound (b) include aliphatic, alicyclic and aromatic polyisocyanates having two or more isocyanate groups, mixtures of two or more of the polyisocyanates, and modifications obtained by modifying these. Polyisocyanate etc. are mentioned.
　イソシアネート基を２以上有する脂肪族系、脂環族系、芳香族系等のポリイソシアネートとしては、ヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、トリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、ポリメチレンポリフェニルポリイソシアネート（通称：クルードＭＤＩまたはポリメリックＭＤＩ）、キシリレンジイソシアネート（ＸＤＩ）等が挙げられる。 Examples of aliphatic, alicyclic and aromatic polyisocyanates having two or more isocyanate groups include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate (MDI). , Polymethylene polyphenyl polyisocyanate (common name: crude MDI or polymeric MDI), xylylene diisocyanate (XDI), and the like.
　変性ポリイソシアネートとしては、前記ポリイソシアネートのプレポリマー型変性体、ヌレート変性体、ビウレット変性体、ウレタン変性体、ウレア変性体、カルボジイミド変性体等が挙げられる。 Examples of the modified polyisocyanate include a prepolymer type modified product, a nurate modified product, a biuret modified product, a urethane modified product, a urea modified product, and a carbodiimide modified product of the polyisocyanate.
　本発明におけるポリイソシアネート化合物（ｂ）としては、なかでも、得られる撥水撥油剤の溶解性の点から、ヘキサメチレンジイソシアネートまたはその変性体が好ましい。
  ポリイソシアネート化合物（ｂ）におけるイソシアネート基含有量は、５～４０質量％が好ましく、１０～３０質量％がより好ましく、１５～３０質量％が最も好ましい。 As the polyisocyanate compound (b) in the present invention, hexamethylene diisocyanate or a modified product thereof is preferable from the viewpoint of the solubility of the obtained water / oil repellent.
The isocyanate group content in the polyisocyanate compound (b) is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and most preferably 15 to 30% by mass.
　＜化合物（ｃ）＞
　本発明における反応生成物には、含フッ素化合物（ａ）以外にも、イソシアネート基と反応性のある活性水素基を有する化合物（ｃ）とポリイソシアネート化合物（ｂ）との反応生成物を含有していてもよく、ポリイソシアネート化合物（ｂ）と、含フッ素化合物（ａ）およびイソシアネート基と反応性のある活性水素基を有する化合物（ｃ）との反応生成物を含有していてもよい。
　活性水素基としては、例えば、水酸基、アミノ基、メルカプト基等が挙げられる。また、イソシアネート基をブロック化しうるブロック化剤であってもよい。さらには、水であってもよい。イソシアネート基と水を反応させると加水分解によりアミノ基が生成するが、生成したアミノ基はさらに別のイソシアネートと反応してウレア結合を形成し、分子中に架橋構造を導入することができる。
　本発明における反応生成物は、化合物（ｃ）がポリイソシアネート化合物（ｂ）のイソシアネート基に対して好ましくは０～５０％反応したものであり、より好ましくは０～３０％反応したものである。かかる範囲を適当に調整して化合物（ｃ）との反応生成物を含有せしめることにより、実質的に本発明の撥水撥油剤の効果（環境に対する負荷が低く撥水撥油性に優れる）を損なわずに、他の特性を付与することができる。化合物（ｃ）として、２種以上を用いてもよい。 <Compound (c)>
In addition to the fluorine-containing compound (a), the reaction product in the present invention contains a reaction product of a compound (c) having an active hydrogen group reactive with an isocyanate group and a polyisocyanate compound (b). It may contain a reaction product of the polyisocyanate compound (b) with the fluorine-containing compound (a) and the compound (c) having an active hydrogen group reactive with an isocyanate group.
Examples of the active hydrogen group include a hydroxyl group, an amino group, a mercapto group, and the like. Moreover, the blocking agent which can block an isocyanate group may be sufficient. Furthermore, water may be used. When an isocyanate group reacts with water, an amino group is generated by hydrolysis. The generated amino group further reacts with another isocyanate to form a urea bond, and a crosslinked structure can be introduced into the molecule.
The reaction product in the present invention is a product obtained by reacting the compound (c) with respect to the isocyanate group of the polyisocyanate compound (b), preferably 0 to 50%, more preferably 0 to 30%. By appropriately adjusting such a range to contain a reaction product with the compound (c), the effect of the water / oil repellent of the present invention is substantially impaired (low environmental load and excellent water / oil repellency). Other properties can be imparted. Two or more kinds of compounds (c) may be used.
　本発明における化合物（ｃ）は、活性水素基を１個有する化合物として、ポリフルオロアルキル基を有するアルコール、直鎖または分岐のアルキルアルコール、水酸基以外の官能基を有するアルコール、アルコール変性シリコーン、ポリオキシアルキレン鎖を有するアルコール等が挙げられる。さらに、活性水素基を複数個有する化合物（多価アルコール）やブロック化剤であってもよい。化合物（ｃ）としては、なかでも、撥水撥油剤の溶媒への溶解性を向上させることが可能であることから活性水素基を１個有する化合物が好ましい。 The compound (c) in the present invention includes a compound having one active hydrogen group as an alcohol having a polyfluoroalkyl group, a linear or branched alkyl alcohol, an alcohol having a functional group other than a hydroxyl group, alcohol-modified silicone, polyoxy Examples include alcohols having an alkylene chain. Further, it may be a compound having a plurality of active hydrogen groups (polyhydric alcohol) or a blocking agent. Among them, the compound (c) is preferably a compound having one active hydrogen group because the solubility of the water / oil repellent in a solvent can be improved.
　化合物（ｃ）として、具体的には、１価のアルコールとして、ＣＦ３ＣＨ２ＯＨ、Ｃ２Ｆ５ＣＨ２ＯＨ、Ｃ２Ｆ５Ｃ３Ｈ６ＯＨ、Ｃ４Ｆ９ＣＨ２ＯＨ、ＨＣ２Ｆ４ＣＨ２ＯＨ、Ｃ６Ｆ１３ＣＨ２ＯＨ、Ｃ４Ｆ９Ｃ２Ｈ４ＯＨ、Ｃ６Ｆ１３Ｃ２Ｈ４ＯＨ、Ｃ４Ｆ９Ｃ３Ｈ６ＯＨ、Ｃ６Ｆ１３Ｃ３Ｈ６ＯＨ、Ｃ４Ｆ９ＳＣ２Ｈ４ＯＨ、Ｃ６Ｆ１３ＳＣ２Ｈ４ＯＨ、Ｃ４Ｆ９ＳＯ２Ｃ２Ｈ４ＯＨ、Ｃ６Ｆ１３ＳＯ２Ｃ２Ｈ４ＯＨ、Ｃ４Ｆ９Ｃ２Ｈ４ＳＣ２Ｈ４ＯＨ、Ｃ６Ｆ１３Ｃ２Ｈ４ＳＣ２Ｈ４ＯＨ、Ｃ４Ｆ９Ｃ２Ｈ４ＳＯ２Ｃ２Ｈ４ＯＨ、Ｃ６Ｆ１３Ｃ２Ｈ４ＳＯ２Ｃ２Ｈ４ＯＨ、Ｃ４Ｆ９ＳＯ２Ｎ（ＣＨ３）Ｃ２Ｈ４ＯＨ、Ｃ６Ｆ１３ＳＯ２Ｎ（ＣＨ３）Ｃ２Ｈ４ＯＨ、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、２－メチル－１－ブタノール、ｔｅｒｔ－ブタノール、１－ヘキサノール、２－エチルヘキサノール、１－オクタノール、ラウリルアルコール、セチルアルコール、ステアリルアルコール、ベヘニルアルコール、エチレングリコールモノアセテート、プロピレングリコールモノアセテート、ジエチレングリコールモノアセテート、ジプロピレングリコールモノアセテート、トリエチレングリコールモノアセテート、ポリエチレングリコールモノアセテート、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ポリエチレングリコールモノエチルエーテル、ヒドロキシアセトン、４－ヒドロキシ－２－ブタノン、片末端アルコール変性シリコーンが挙げられる。 As the compound (c), specifically, as a monovalent alcohol, CF 3 CH 2 OH, C 2 F 5 CH 2 OH, C 2 F 5 C 3 H 6 OH, C 4 F 9 CH 2 OH, HC 2 F 4 CH 2 OH, C 6 F 13 CH 2 OH, C 4 F 9 C 2 H 4 OH, C 6 F 13 C 2 H 4 OH, C 4 F 9 C 3 H 6 OH, C 6 F 13 C 3 H 6 OH, C 4 F 9 SC 2 H 4 OH, C 6 F 13 SC 2 H 4 OH, C 4 F 9 SO 2 C 2 H 4 OH, C 6 F 13 SO 2 C 2 H 4 OH, C 4 F 9 C 2 H 4 SC 2 H 4 OH, C 6 F 13 C 2 H 4 SC 2 H 4 OH, C 4 F 9 C 2 H 4 SO 2 C 2 H 4 OH, C 6 F 13 C 2 H 4 SO 2 C 2 H 4 OH , C 4 F 9 SO 2 N (CH 3) C 2 H 4 H, C 6 F 13 SO 2 N (CH 3) C 2 H 4 OH, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, tert- butanol 1-hexanol, 2-ethylhexanol, 1-octanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol monoacetate , Polyethylene glycol monoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether Tellurium, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, polyethylene glycol monoethyl ether, hydroxyacetone, 4-hydroxy-2-butanone, one-end alcohol-modified Silicone may be mentioned.
　活性水素基としてアミノ基を１個有する化合物には、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ヘキシルアミン、オクチルアミン、ドデシルアミン、セチルアミン、ステアリルアミン、ベヘニルアミン、ジエチルアミン、ジブチルアミンが挙げられる。 Examples of the compound having one amino group as an active hydrogen group include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, dodecylamine, cetylamine, stearylamine, behenylamine, diethylamine and dibutylamine.
　多価のアルコールとしては、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，４－ブタンジオール、２，３－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、グリセリン、ペンタエリスリトール、ジペンタエリスリトール、単糖類、二糖類、オリゴ糖類等を挙げることができる。 Examples of polyhydric alcohols include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and triethylene glycol. , Tetraethylene glycol, polyethylene glycol, dipropylene glycol, glycerin, pentaerythritol, dipentaerythritol, monosaccharide, disaccharide, oligosaccharide and the like.
　アミノ基を含有する化合物としては、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン等が挙げられる。 Examples of the compound containing an amino group include ethylenediamine, propylenediamine, and hexamethylenediamine.
　ブロック化剤としては、３，５－ジメチルピラゾール、アセトキシム、メチルエチルケトオキシム、ベンゾフェノンオキシム、チオフェノール、ヒドロキシルアミン、１級アミノメルカプタン、２級アミノメルカプタン等が挙げられる。特に好ましくは、メチルエチルケトオキシムまたは３，５－ジメチルピラゾールである。 Examples of the blocking agent include 3,5-dimethylpyrazole, acetoxime, methyl ethyl ketoxime, benzophenone oxime, thiophenol, hydroxylamine, primary amino mercaptan, secondary amino mercaptan, and the like. Particularly preferred is methyl ethyl ketoxime or 3,5-dimethylpyrazole.
　化合物（ｃ）は、上記１種を単独で用いてもよく、２種以上を併用してもよい。 Compound (c) may be used alone or in combination of two or more.
　＜反応生成物の製造方法＞
　本発明における反応生成物は、含フッ素化合物（ａ）とポリイソシアネート化合物（ｂ）を反応させることによって得られる。含フッ素化合物（ａ）以外の化合物（ｃ）も反応させる場合、ポリイソシアネート化合物（ｂ）に、含フッ素化合物（ａ）と化合物（ｃ）を順次反応させる、または含フッ素化合物（ａ）と化合物（ｃ）の混合物を反応させる製造方法である。反応の際には、適宜触媒および反応溶媒を用いることができる。 <Method for producing reaction product>
The reaction product in the present invention can be obtained by reacting the fluorine-containing compound (a) with the polyisocyanate compound (b). When the compound (c) other than the fluorine-containing compound (a) is also reacted, the fluorine-containing compound (a) and the compound (c) are sequentially reacted with the polyisocyanate compound (b), or the fluorine-containing compound (a) and the compound are reacted. It is a manufacturing method with which the mixture of (c) is made to react. In the reaction, a catalyst and a reaction solvent can be appropriately used.
　本発明における反応生成物には、含フッ素化合物（ａ）のＺがアミノ基（ＮＨ２）の場合、反応条件によっては生成物であるウレタン結合やウレア結合の水素原子ともさらに反応させた反応生成物を含んでもよい。 In the reaction product in the present invention, when Z of the fluorine-containing compound (a) is an amino group (NH 2 ), depending on the reaction conditions, the reaction product further reacted with a hydrogen atom of a urethane bond or urea bond as a product. You may include things.
　本発明において、含フッ素化合物（ａ）およびポリイソシアネート化合物（ｂ）の割合は、含フッ素化合物（ａ）の活性水素基（水酸基、アミノ基、メルカプト基等）と、ポリイソシアネート化合物（ｂ）中のイソシアネート基のモル数が、１：１となるように調整することが好ましい。化合物（ｃ）も反応させる場合は、含フッ素化合物（ａ）と化合物（ｃ）の活性水素基の合計と、ポリイソシアネート化合物（ｂ）中のイソシアネート基のモル数が、１：１となるように調整することが好ましい。 In the present invention, the proportions of the fluorine-containing compound (a) and the polyisocyanate compound (b) are the active hydrogen groups (hydroxyl group, amino group, mercapto group, etc.) of the fluorine-containing compound (a) and the polyisocyanate compound (b). It is preferable to adjust the number of moles of the isocyanate group to be 1: 1. When the compound (c) is also reacted, the total number of active hydrogen groups of the fluorine-containing compound (a) and the compound (c) and the number of moles of isocyanate groups in the polyisocyanate compound (b) are 1: 1. It is preferable to adjust to.
　含フッ素化合物（ａ）および化合物（ｃ）とポリイソシアネート化合物（ｂ）の反応生成物は、未反応の含フッ素化合物（ａ）、化合物（ｃ）を含有していてもよく、ポリイソシアネート化合物（ｂ）のイソシアネート基の一部が未反応であっても良いが、好ましくは含フッ素化合物（ａ）および化合物（ｃ）はそれらの総量にたいして８０％以上がイソシアネート基と反応していることが好ましく、ポリイソシアネート化合物（ｂ）のイソシアネート基はその８０％以上が反応していることが好ましい。 The fluorine-containing compound (a) and the reaction product of the compound (c) and the polyisocyanate compound (b) may contain the unreacted fluorine-containing compound (a) and the compound (c). Although a part of the isocyanate group of b) may be unreacted, it is preferable that 80% or more of the fluorine-containing compound (a) and the compound (c) are reacted with the isocyanate group based on the total amount thereof. 80% or more of the isocyanate groups of the polyisocyanate compound (b) are preferably reacted.
　イソシアネート基を有しない反応生成物を製造する場合、上記のように活性水素基とイソシアネート基の割合を調整して反応生成物を製造することはもちろん、製造した反応生成物のイソシアネート基を検出し、反応生成物が有するイソシアネート基を好ましくは５％以下、より好ましくは、実質上ゼロにされる。反応生成物中にイソシアネート基が存在した場合は化合物（ｃ）などを添加してさらにイソシアネート基が検出されなくなるまで反応させる方法を使用して目的とする反応生成物を製造することができる。 When producing a reaction product having no isocyanate group, the reaction product is produced by adjusting the ratio of the active hydrogen group and the isocyanate group as described above, as well as detecting the isocyanate group of the produced reaction product. The isocyanate group of the reaction product is preferably 5% or less, more preferably substantially zero. When an isocyanate group is present in the reaction product, the desired reaction product can be produced using a method in which compound (c) or the like is added and the reaction is continued until no isocyanate group is detected.
　反応生成物の製造において、触媒として、３級アミン（トリエチルアミン、ビス（２－ジメチルアミノエチル）エーテル、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルヘキサメチレンジアミン等。）、カルボン酸金属塩（酢酸カリウム、２－エチルヘキサン酸カリウム等。）、有機金属化合物（ジブチルすずジラウレート等。）等を用いることができる。特に、トリエチルアミン、またはジブチルすずジラウレートが好ましい。触媒の量は、原料混合物（含フッ素化合物（ａ）、ポリイソシアネート化合物（ｂ）、化合物（ｃ）の合計）１００質量部に対して０．００１～５質量部がよい。 In the production of the reaction product, a tertiary amine (triethylamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine, etc.), carboxylic acid metal salt ( Potassium acetate, potassium 2-ethylhexanoate, etc.), organometallic compounds (dibutyltin dilaurate, etc.) and the like can be used. In particular, triethylamine or dibutyltin dilaurate is preferable. The amount of the catalyst is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the raw material mixture (the total of the fluorine-containing compound (a), the polyisocyanate compound (b) and the compound (c)).
　反応溶媒としては、イソシアネート基と反応しうる活性水素基を有さなければ特に限定されず、ハロゲン化合物、炭化水素、ケトン、エステル、エーテル、窒素化合物、硫黄等が用いられる。 The reaction solvent is not particularly limited as long as it does not have an active hydrogen group capable of reacting with an isocyanate group, and halogen compounds, hydrocarbons, ketones, esters, ethers, nitrogen compounds, sulfur and the like are used.
　ハロゲン化合物としては、ハロゲン化炭化水素、ハロゲン化エーテル等が挙げられる。ハロゲン化炭化水素としては、ハイドロクロロフルオロカーボン、ハイドロフルオロカーボン、塩素化炭化水素等が挙げられる。ハイドロクロロフルオロカーボンとしては、ＣＨ３ＣＣｌ２Ｆ、ＣＨＣｌ２ＣＦ２ＣＦ３、ＣＨＣｌＦＣＦ２ＣＣｌＦ２等が挙げられる。ハイドロフルオロカーボンとしては、ＣＦ３ＣＨＦＣＨＦＣＦ２ＣＦ３、ＣＦ３（ＣＦ２）４ＣＨＦ２、ＣＦ３ＣＦ２ＣＦ２ＣＨ２ＣＨ２ＣＨ３、ＣＦ３（ＣＦ２）５ＣＨ２ＣＨ３、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン等が挙げられる。 Examples of the halogen compound include halogenated hydrocarbons and halogenated ethers. Examples of the halogenated hydrocarbon include hydrochlorofluorocarbon, hydrofluorocarbon, chlorinated hydrocarbon and the like. The hydrochlorofluorocarbon, CH 3 CCl 2 F, CHCl 2 CF 2 CF 3, CHClFCF 2 CClF 2 , and the like. Examples of the hydrofluorocarbon include CF 3 CHFCHFCF 2 CF 3 , CF 3 (CF 2 ) 4 CHF 2 , CF 3 CF 2 CF 2 CH 2 CH 2 CH 3 , CF 3 (CF 2 ) 5 CH 2 CH 3 , 1,1 2,2,3,3,4-heptafluorocyclopentane and the like.
　ハロゲン化エーテルとしては、ハイドロフルオロアルキルエーテル、ハイドロフルオロ（アルキルアルケニルエーテル）、ハイドロフルオロ環状エーテル等が挙げられる。ハイドロフルオロアルキルエーテルとしては、分離型ハイドロフルオロアルキルエーテル、非分離型ハイドロフルオロアルキルエーテル等が挙げられる。分離型ハイドロフルオロエーテルとは、エーテル性酸素原子の一方にＲＦ基、他方にアルキル基が結合している化合物である。非分離型ハイドロフルオロアルキルエーテルとは、エーテル性酸素原子の両側に部分的にフッ素化されたアルキル基が結合している化合物である。 Examples of the halogenated ether include hydrofluoroalkyl ether, hydrofluoro (alkyl alkenyl ether), hydrofluoro cyclic ether and the like. Examples of hydrofluoroalkyl ethers include separated hydrofluoroalkyl ethers and non-separated hydrofluoroalkyl ethers. The separate type hydrofluoroether is a compound in which one to R F group of etheric oxygen atom, an alkyl group at the other attached. Non-separable hydrofluoroalkyl ether is a compound in which partially fluorinated alkyl groups are bonded to both sides of an etheric oxygen atom.
　分離型ハイドロフルオロアルキルエーテルとしては、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＯＣＨ３、（ＣＦ３）２ＣＦＣＦ２ＯＣＨ３、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＯＣＨ２ＣＨ３、（ＣＦ３）２ＣＦＣＦ２ＯＣＨ２ＣＨ３、ＣＦ３ＣＦ２ＣＦ（ＯＣＨ３）ＣＦ（ＣＦ３）２、ＣＦ３ＣＦ２ＣＦ（ＯＣＨ２ＣＨ３）ＣＦ（ＣＦ３）２、Ｃ３Ｈ７ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＨ３が挙げられる。非分離型ハイドロフルオロアルキルエーテルとしては、ＣＨＦ２ＣＦ２ＯＣＨ２ＣＦ３、ＣＦ３ＣＦ２ＣＨ２ＯＣＦ２ＣＨＦ２等が挙げられる。塩素化炭化水素としては、塩化メチレン、クロロホルム、１，１，１－トリクロロエタン、ジクロロエチレン、トリクロロエチレン、テトラクロロエチレン等が挙げられる。 Examples of the separated hydrofluoroalkyl ether include CF 3 CF 2 CF 2 CF 2 OCH 3 , (CF 3 ) 2 CFCF 2 OCH 3 , CF 3 CF 2 CF 2 CF 2 OCH 2 CH 3 , and (CF 3 ) 2 CFCF 2. OCH 2 CH 3, CF 3 CF 2 CF (OCH 3) CF (CF 3) 2, CF 3 CF 2 CF (OCH 2 CH 3) CF (CF 3) 2, C 3 H 7 OCF (CF 3) CF 2 OCH 3 is mentioned. Examples of the non-separable hydrofluoroalkyl ether include CHF 2 CF 2 OCH 2 CF 3 and CF 3 CF 2 CH 2 OCF 2 CHF 2 . Examples of the chlorinated hydrocarbon include methylene chloride, chloroform, 1,1,1-trichloroethane, dichloroethylene, trichloroethylene, and tetrachloroethylene.
　炭化水素としては、脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素等が挙げられる。脂肪族炭化水素としては、ペンタン、２－メチルブタン、３－メチルペンタン、ヘキサン、２，２－ジメチルブタン、２，３－ジメチルブタン、ヘプタン、オクタン、２，２，４－トリメチルペンタン、２，２，３－トリメチルヘキサン、デカン、ウンデカン、ドデカン、２，２，４，６，６－ペンタメチルヘプタン、トリデカン、テトラデカン、ヘキサデカン等が挙げられる。脂環式炭化水素としては、シクロペンタン、メチルシクロペンタン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等が挙げられる。 Examples of hydrocarbons include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. Aliphatic hydrocarbons include pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,4-trimethylpentane, 2,2 , 3-trimethylhexane, decane, undecane, dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, tetradecane, hexadecane and the like. Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
　芳香族炭化水素としては、ベンゼン、トルエン、キシレン等が挙げられる。
  ケトンとしては、アセトン、メチルエチルケトン、２－ペンタノン、３－ペンタノン、２－ヘキサノン、メチルイソブチルケトン（以下、ＭＩＢＫと記す。）等が挙げられる。
  エステルとしては、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等が挙げられる。
  エーテルとしては、メチルｔｅｒｔ－ブチルエーテル、ジイソプロピルエーテル、シクロペンチルメチルエーテルなどのアルキルエーテル、ジオキサン、テトラヒドロフランなどの環状エーテル等が挙げられる。 Examples of aromatic hydrocarbons include benzene, toluene, xylene and the like.
Examples of the ketone include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone (hereinafter referred to as MIBK), and the like.
Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, and methyl propionate.
Examples of the ether include alkyl ethers such as methyl tert-butyl ether, diisopropyl ether and cyclopentyl methyl ether, and cyclic ethers such as dioxane and tetrahydrofuran.
　窒素化合物としては、ピリジン、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン等が挙げられる。硫黄化合物としては、ジメチルスルホキシド、スルホラン等が挙げられる。
  反応溶媒としては、特に、溶解性の観点から、クロロホルム、メチルエチルケトン、ＭＩＢＫ、シクロヘキサノン、ＤＭＦが好ましい。反応溶媒は、上記１種を単独で用いてもよく、２種以上を併用して用いてもよい。 Examples of the nitrogen compound include pyridine, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methylpyrrolidone and the like. Examples of the sulfur compound include dimethyl sulfoxide and sulfolane.
As the reaction solvent, chloroform, methyl ethyl ketone, MIBK, cyclohexanone, and DMF are particularly preferable from the viewpoint of solubility. As the reaction solvent, one of the above may be used alone, or two or more may be used in combination.
　反応生成物の製造方法において、反応溶媒中の原料混合物濃度は、５～１００質量％が好ましく、１０～９０質量％がより好ましく、２０～８０質量％が特に好ましい。反応は無水条件で行われることが副反応を抑制するために好ましい。
  反応温度としては、０～２００℃、好ましくは２０～８０℃が採用される。反応時間は１～２００時間が好ましい。 In the method for producing a reaction product, the concentration of the raw material mixture in the reaction solvent is preferably 5 to 100% by mass, more preferably 10 to 90% by mass, and particularly preferably 20 to 80% by mass. The reaction is preferably performed under anhydrous conditions in order to suppress side reactions.
The reaction temperature is 0 to 200 ° C., preferably 20 to 80 ° C. The reaction time is preferably 1 to 200 hours.
　反応の終了は、フーリエ変換赤外分光光度計（ＦＴ－ＩＲ）測定により、イソシアネート基に由来する２２８０ｃｍ－１付近のピークの消失により確認することができる。例えば、反応溶液の１滴をＫＢｒ窓材にたらしてはさみ、透過型ＦＴ－ＩＲ測定を行うことで確認することができる。あるいは、反応溶液の一部を取り、真空乾燥により溶媒を除去して反応生成物の固体を得、反射型ＦＴ－ＩＲ測定を行うことによっても反応の終了を確認することができる。本発明の撥水撥油剤としては、イソシアネート基を有しない（すなわち、この測定によりイソシアネート基が検出されない）反応生成物であることが好ましい。 The completion of the reaction can be confirmed by disappearance of a peak around 2280 cm −1 derived from an isocyanate group by Fourier transform infrared spectrophotometer (FT-IR) measurement. For example, it can be confirmed by placing one drop of the reaction solution on a KBr window material and performing transmission type FT-IR measurement. Alternatively, the completion of the reaction can also be confirmed by taking a part of the reaction solution, removing the solvent by vacuum drying to obtain a reaction product solid, and performing reflection type FT-IR measurement. The water / oil repellent of the present invention is preferably a reaction product having no isocyanate group (that is, no isocyanate group is detected by this measurement).
　＜撥水撥油剤組成物＞
　本発明の撥水撥油剤組成物は、前記撥水撥油剤と溶媒と、必要に応じて界面活性剤および添加剤を含む組成物である。本発明の撥水撥油剤組成物の形態としては、撥水撥油剤が溶媒中に溶解している、または微粒子として分散している形態であることが好ましい。 <Water / oil repellent composition>
The water / oil repellent composition of the present invention is a composition comprising the water / oil repellent, a solvent, and optionally a surfactant and an additive. The form of the water / oil repellent composition of the present invention is preferably a form in which the water / oil repellent is dissolved in a solvent or dispersed as fine particles.
　本発明の撥水撥油剤組成物は、下記（ｉ）、（ｉｉ）、（ｉｉｉ）または（ｉｖ）の方法で製造される。
（ｉ）上記反応溶媒を使用した製法により撥水撥油剤の溶液を得た後、他の溶媒、必要に応じて添加剤を加える方法。
（ｉｉ）上記反応溶媒を使用した製法により撥水撥油剤の溶液を得た後、撥水撥油剤を分離し、撥水撥油剤に溶媒、必要に応じて添加剤を加える方法。
（ｉｉｉ）上記反応溶媒を使用した製法により撥水撥油剤の溶液を得た後、他の溶媒、界面活性剤、必要に応じて添加剤を加え、必要に応じて脱溶媒する方法。
（ｉｖ）上記反応溶媒を使用した製法により撥水撥油剤の溶液を得た後、撥水撥油剤を分離し、撥水撥油剤に溶媒、界面活性剤、必要に応じて添加剤を加え、必要に応じて脱溶媒する方法。 The water / oil repellent composition of the present invention is produced by the following method (i), (ii), (iii) or (iv).
(I) A method in which a solution of a water / oil repellent agent is obtained by a production method using the reaction solvent, and then another solvent and, if necessary, an additive are added.
(Ii) A method of obtaining a water / oil repellent solution by a method using the reaction solvent, separating the water / oil repellent, and adding a solvent and, if necessary, an additive to the water / oil repellent.
(Iii) A method of obtaining a water / oil repellent solution by a production method using the reaction solvent, adding another solvent, a surfactant, and an additive as necessary, and removing the solvent as necessary.
(Iv) After obtaining a water / oil repellent solution by a method using the reaction solvent, the water / oil repellent is separated, and a solvent, a surfactant, and an additive as necessary are added to the water / oil repellent, A method of removing the solvent as necessary.
　本発明における溶媒としては、具体的に、前述した反応溶媒の他に、水、アルコール、グリコール、グリコールエーテル等が挙げられる。撥水撥油剤組成物が溶液の場合には、特に、溶解性、取り扱いの容易さからハロゲン化合物、ケトン、エステルが好ましい。撥水撥油剤組成物が分散液の場合には、特に、溶解性、取り扱いの容易さから水、アルコール、グリコール、グリコールエーテルからなる１種以上の媒体が好ましい。 Specific examples of the solvent in the present invention include water, alcohol, glycol, glycol ether and the like in addition to the reaction solvent described above. When the water / oil repellent composition is a solution, a halogen compound, a ketone, or an ester is particularly preferred from the viewpoint of solubility and ease of handling. When the water / oil repellent composition is a dispersion, at least one medium composed of water, alcohol, glycol, glycol ether is particularly preferred in view of solubility and ease of handling.
　アルコールとしては、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、２－メチルプロパノール、１，１－ジメチルエタノール、１－ペンタノール、２－ペンタノール、３－ペンタノール、２－メチル－１－ブタノール、３－メチル－１－ブタノール、１，１－ジメチルプロパノール、３－メチル－２－ブタノール、１，２－ジメチルプロパノール、１－ヘキサノール、２－メチル－１－ペンタノール、４－メチル－２－ペンタノール、２－エチル－１－ブタノール、１－へプタノール、２－へプタノール、３－へプタノール等が挙げられる。 Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, and 3-pentanol. 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-butanol, 1,2-dimethylpropanol, 1-hexanol, 2-methyl-1-pen Examples include butanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, and 3-heptanol.
　グリコール、グリコールエーテルとしては、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセタート、エチレングリコールモノエチルエーテルアセタート、エチレングリコールモノブチルエーテルアセタート、プロピレングリコール、グリコールエーテルとしては、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールジメチルエーテル、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコール、トリプロピレングリコールモノメチルエーテル、ポリプロピレングリコール、ヘキシレングリコール等が挙げられる。 As glycol and glycol ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol , Glycol ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol B propylene glycol monomethyl ether, polypropylene glycol, hexylene glycol, and the like.
　反応溶媒中における撥水撥油剤の固形分濃度は、上記撥水撥油剤組成物の好ましい製造方法によれば、溶液（１００質量％）中に５～１００質量％が好ましく、１０～９０質量％がより好ましく、２０～８０質量％が特に好ましい。
  なお、前記固形分濃度は、撥水撥油剤の他、界面活性剤（乳化剤）も含む濃度である。ここで、固形分濃度とは、加熱前の撥水撥油剤組成物の質量と、１２０℃の対流式乾燥機にて４時間乾燥した後の質量とから計算される。 The solid content concentration of the water / oil repellent in the reaction solvent is preferably 5 to 100% by weight in the solution (100% by weight), preferably 10 to 90% by weight, according to the preferred method for producing the water / oil repellent composition. Is more preferable, and 20 to 80% by mass is particularly preferable.
The solid content concentration is a concentration including a surfactant (emulsifier) in addition to the water / oil repellent. Here, the solid content concentration is calculated from the mass of the water / oil repellent composition before heating and the mass after drying in a convection dryer at 120 ° C. for 4 hours.
　上述の本発明の反応生成物の製造方法により得られた撥水撥油剤を含有する反応溶液を本発明の撥水撥油剤組成物として用いるには、撥水撥油剤を撥水撥油剤組成物として好ましい固形分濃度０．０５～１０質量％、より好ましくは０．１～５質量％となるように、適宜希釈成分等を加え、調整すればよい。 In order to use the reaction solution containing the water / oil repellent obtained by the method for producing the reaction product of the present invention as the water / oil repellent composition of the present invention, the water / oil repellent is used as the water / oil repellent composition. In order to achieve a preferable solid content concentration of 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, a dilution component or the like may be appropriately added and adjusted.
　本発明の撥水撥油剤組成物の形態が分散液の場合、撥水撥油剤または撥水撥油剤を含む溶液、界面活性剤および任意成分を秤量し、適当量の溶媒とともに、ホモミキサー、高圧乳化機等で均一に攪拌して分散液とする等の通常の方法が用いられる。 When the form of the water / oil repellent composition of the present invention is a dispersion, a water / oil repellent or a solution containing a water / oil repellent, a surfactant and an optional component are weighed, together with an appropriate amount of solvent, a homomixer, a high pressure A usual method such as uniform stirring with an emulsifier or the like to form a dispersion is used.
　分散液型の撥水撥油剤組成物中の撥水撥油剤の平均粒子径は、１０～１０００ｎｍが好ましく、１０～３００ｎｍがより好ましく、１０～２５０ｎｍが特に好ましい。平均粒子径が該範囲であれば、界面活性剤等を多量に用いる必要がなく、撥水性が良好であり、染色された布帛類を処理した場合に色落ちが発生せず、媒体中で分散粒子が安定に存在できて沈降することがない。分散液の平均粒子径は、動的光散乱装置、電子顕微鏡等により測定でき、上記平均粒子径は動的光散乱装置で測定した値である。 The average particle size of the water / oil repellent in the dispersion type water / oil repellent composition is preferably 10 to 1000 nm, more preferably 10 to 300 nm, and particularly preferably 10 to 250 nm. If the average particle size is in this range, it is not necessary to use a large amount of a surfactant, etc., water repellency is good, no discoloration occurs when dyed fabrics are processed, and dispersion in the medium The particles can exist stably and do not settle. The average particle diameter of the dispersion can be measured with a dynamic light scattering apparatus, an electron microscope, or the like, and the average particle diameter is a value measured with a dynamic light scattering apparatus.
　なお、撥水撥油剤を上述した好ましい範囲の粒子径で分散させるためには、界面活性剤の種類および量、ホモミキサーの回転数、高圧乳化時の圧力等の条件を調節すればよい。 In addition, in order to disperse the water / oil repellent with a particle diameter in the preferred range described above, conditions such as the type and amount of the surfactant, the rotation speed of the homomixer, and the pressure during high-pressure emulsification may be adjusted.
　界面活性剤としては、炭化水素系界面活性剤またはフッ素系界面活性剤が挙げられ、それぞれ、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、または両性界面活性剤が挙げられる。 Examples of the surfactant include a hydrocarbon-based surfactant and a fluorine-based surfactant, and an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant, respectively. .
　界面活性剤としては、分散安定性の点から、ノニオン性界面活性剤とカチオン性界面活性剤または両性界面活性剤との併用、または、アニオン性界面活性剤の単独が好ましく、ノニオン性界面活性剤とカチオン性界面活性剤との併用が好ましい。 As the surfactant, from the viewpoint of dispersion stability, a combination of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant, or an anionic surfactant alone is preferable, and a nonionic surfactant is preferable. And a cationic surfactant are preferred.
　界面活性剤の合計量は、撥水撥油剤（１００質量部）に対して１～２０質量部が好ましく、１～１５質量部より好ましい。 The total amount of the surfactant is preferably 1 to 20 parts by mass and more preferably 1 to 15 parts by mass with respect to the water / oil repellent (100 parts by mass).
　添加剤としては、浸透剤、消泡剤、吸水剤、帯電防止剤、制電性重合体、防皺剤、風合い調整剤、造膜助剤、水溶性高分子（ポリアクリルアミド、ポリビニルアルコール等。）、熱硬化剤（メラミン樹脂、ウレタン樹脂、トリアジン環含有化合物、イソシアネート系化合物等。）、エポキシ硬化剤（イソフタル酸ジヒドラジド、アジピン酸ジヒドラジド、セバチン酸ジヒドラジド、ドデカン二酸ジヒドラジド、１，６－ヘキサメチレンビス（Ｎ，Ｎ－ジメチルセミカルバジド）、１，１，１’，１’－テトラメチル－４，４’－（メチレン－ジ－パラ－フェニレン）ジセミカルバジド、スピログリコール等。）、熱硬化触媒、架橋触媒、合成樹脂、繊維安定剤、無機微粒子等が挙げられる。 Additives include penetrants, antifoaming agents, water absorbing agents, antistatic agents, antistatic polymers, antifungal agents, texture modifiers, film-forming aids, water-soluble polymers (polyacrylamide, polyvinyl alcohol, etc.). ), Thermosetting agent (melamine resin, urethane resin, triazine ring-containing compound, isocyanate compound, etc.), epoxy curing agent (isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, 1,6-hexa Methylene bis (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-para-phenylene) disemicarbazide, spiroglycol, etc.), thermosetting catalyst , Crosslinking catalysts, synthetic resins, fiber stabilizers, inorganic fine particles, and the like.
　添加剤の量は、撥水撥油剤（１００質量部）に対して０～５０質量％が好ましく、０～２０質量％がより好ましい。 The amount of the additive is preferably 0 to 50% by mass and more preferably 0 to 20% by mass with respect to the water / oil repellent (100 parts by mass).
　本発明の撥水撥油剤組成物は、必要に応じて、本発明の撥水撥油剤以外の、撥水性および／または撥油性を発現できる共重合体（たとえば、市販の撥水剤、市販の撥油剤、市販の撥水撥油剤等。）、フッ素原子を有さない撥水性化合物等を含んでいてもよい。フッ素原子を有さない撥水性化合物としては、パラフィン系化合物、脂肪族アマイド系化合物、アルキルエチレン尿素化合物、シリコーン系化合物等が挙げられる。 If necessary, the water / oil repellent composition of the present invention may be a copolymer that exhibits water repellency and / or oil repellency other than the water / oil repellent of the present invention (for example, a commercially available water repellent, a commercially available water repellent, Oil repellent, commercially available water / oil repellent, etc.), water repellent compounds having no fluorine atom, and the like. Examples of the water repellent compound having no fluorine atom include paraffinic compounds, aliphatic amide compounds, alkylethyleneurea compounds, silicone compounds, and the like.
　本発明の撥水撥油剤組成物で処理可能な物品は特に限定されるものではなく、種々の例をあげることができる。例えば、繊維（天然繊維、合成繊維、混紡繊維等。）、各種繊維製品、不織布、樹脂、紙、皮革、金属、石、コンクリート、石膏、ガラス等に使用することができる。好ましい用途として合成皮革、カーペット、カーテン、壁紙、車輌の内装品等が挙げられる。 The article that can be treated with the water / oil repellent composition of the present invention is not particularly limited, and various examples can be given. For example, it can be used for fibers (natural fibers, synthetic fibers, blended fibers, etc.), various fiber products, nonwoven fabrics, resins, paper, leather, metals, stones, concrete, gypsum, glass and the like. Preferred applications include synthetic leather, carpets, curtains, wallpaper, vehicle interiors, and the like.
　処理方法としては、たとえば、公知の塗工方法によって物品に撥水撥油剤組成物を塗布または含浸した後、乾燥する方法が挙げられる。さらに、帯電防止加工、柔軟加工、抗菌加工、消臭加工、防水加工等を行ってもよい。防水加工としては、防水膜を付与する加工が挙げられる。防水膜としては、ウレタン樹脂やアクリル樹脂から得られる多孔質膜、ウレタン樹脂やアクリル樹脂から得られる無孔質膜、ポリテトラフルオロエチレン膜、またはこれらを組み合わせた透湿防水膜が挙げられる。 Examples of the treatment method include a method of applying or impregnating an article with a water / oil repellent composition by a known coating method and then drying. Furthermore, you may perform an antistatic process, a flexible process, an antibacterial process, a deodorizing process, a waterproof process, etc. Examples of waterproofing include processing for providing a waterproof film. Examples of the waterproof membrane include a porous membrane obtained from a urethane resin or an acrylic resin, a nonporous membrane obtained from a urethane resin or an acrylic resin, a polytetrafluoroethylene membrane, or a moisture-permeable waterproof membrane combining these.
　本発明の撥水撥油剤は、アルコールとして炭素数６以下のポリフルオロアルキル部分を有する含フッ素化合物とポリイソシアネート化合物を反応させた反応生成物を含有するものであり、物品に処理することで環境負荷が小さく、かつ十分な撥水撥油性を付与するものである。本発明の撥水撥油剤組成物を用いて上記物品を処理すると、高品位な撥水撥油性を物品に付与できる。 The water / oil repellent of the present invention contains a reaction product obtained by reacting a fluorine-containing compound having a polyfluoroalkyl moiety having 6 or less carbon atoms as an alcohol with a polyisocyanate compound, and is treated with an article to treat the environment. The load is small and sufficient water and oil repellency is imparted. When the article is treated with the water / oil repellent composition of the present invention, high quality water / oil repellency can be imparted to the article.
　本発明を実施例、比較例により具体的に説明するが、本発明はこれらに限定されない。 The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto.
　［化合物（ａ１）の合成］
　撹拌機を備えた反応器（内容積５００ｍＬ、ガラス製）に、窒素雰囲気下、４－ヒドロキシ安息香酸（１３５．０ｇ）、４－トルエンスルホン酸１水和物（９．３０ｇ）、およびＣ６Ｆ１３ＣＨ２ＣＨ２ＯＨ（５３３．８ｇ）を投入して撹拌した。つづいて反応器の内温が１４０℃になるように加熱し、反応器を減圧（０～－０．０５ＭＰａ）にして水を留去しながら６時間撹拌した。さらに反応器の内温を１１０℃に下げ、さらに減圧にして過剰のＣ６Ｆ１３ＣＨ２ＣＨ２ＯＨを留去した。 [Synthesis of Compound (a1)]
To a reactor equipped with a stirrer (internal volume 500 mL, glass), under a nitrogen atmosphere, 4-hydroxybenzoic acid (135.0 g), 4-toluenesulfonic acid monohydrate (9.30 g), and C 6 F 13 CH 2 CH 2 OH (533.8 g) was added and stirred. Subsequently, the internal temperature of the reactor was heated to 140 ° C., and the reactor was reduced in pressure (0 to −0.05 MPa) and stirred for 6 hours while distilling off water. Furthermore, the internal temperature of the reactor was lowered to 110 ° C., and the pressure was further reduced to distill off excess C 6 F 13 CH 2 CH 2 OH.
　得られた白色固体を酢酸エチル９００ｍＬに溶解して分液ロートに移し、イオン交換水（１２００ｍＬ）で２回洗浄し、酢酸エチル層の溶媒を留去することにより、４６０．８ｇの下記化合物（ａ１）（白色固体）を得た。収率は９８％であった。 The obtained white solid was dissolved in 900 mL of ethyl acetate, transferred to a separatory funnel, washed twice with ion-exchanged water (1200 mL), and the solvent of the ethyl acetate layer was distilled off to remove 460.8 g of the following compound ( a1) (white solid) was obtained. The yield was 98%.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　得られた化合物（ａ１）の１Ｈ－ＮＭＲの測定結果を以下に示す。なお、各測定値は、測定値に続く（）内に示す基に由来する測定値を意味するが、この基に［］で囲まれた部分がある場合は、測定値は［］で囲まれた部分に由来する測定値を意味するものである。以下，実施例で示すＮＭＲの測定結果については、全て同様である。 The measurement result of 1 H-NMR of the obtained compound (a1) is shown below. Each measured value means a measured value derived from the group shown in parentheses following the measured value. If there is a part surrounded by [] in this group, the measured value is surrounded by []. It means the measured value derived from the part. Hereinafter, the NMR measurement results shown in the examples are all the same.
　１Ｈ－ＮＭＲ（溶媒：ＣＤ３ＣＯＣＤ３）δ（ｐｐｍ）：２．８１（２Ｈ、ｍ、－ＣＨ２ＣＦ２－）、４．６２（２Ｈ、ｔ、－ＣＯＯ［ＣＨ２］ＣＨ２－）、６．９４（２Ｈ、ｄ、Ｐｈ）、７．９１（２Ｈ、ｄ、Ｐｈ）、９．２１（１Ｈ、ｓ、－ＯＨ）。 1 H-NMR (solvent: CD 3 COCD 3 ) δ (ppm): 2.81 (2H, m, —CH 2 CF 2 —), 4.62 (2H, t, —COO [CH 2 ] CH 2 — ), 6.94 (2H, d, Ph), 7.91 (2H, d, Ph), 9.21 (1H, s, -OH).
　［化合物（ａ２）の合成］
　撹拌機を備えた反応器（内容積５００ｍＬ、ガラス製）に、窒素雰囲気下、４－アミノ安息香酸エチル（１００．０ｇ）、炭酸カリウム（８．３７ｇ）、およびＣ６Ｆ１３ＣＨ２ＣＨ２ＯＨ（４４０．８ｇ）を投入して撹拌した。つづいて反応器の内温が１２０℃になるように加熱し、反応器を減圧（０～－０．０５ＭＰａ）にしてエタノールを留去しながら１２時間撹拌した。さらに減圧にして過剰のＣ６Ｆ１３ＣＨ２ＣＨ２ＯＨを留去した。 [Synthesis of Compound (a2)]
A reactor equipped with a stirrer (internal volume 500 mL, glass) was charged with ethyl 4-aminobenzoate (100.0 g), potassium carbonate (8.37 g), and C 6 F 13 CH 2 CH 2 under a nitrogen atmosphere. OH (440.8 g) was added and stirred. Subsequently, the reactor was heated to an internal temperature of 120 ° C., and the reactor was depressurized (0 to −0.05 MPa) and stirred for 12 hours while distilling off ethanol. Further, the pressure was reduced to remove excess C 6 F 13 CH 2 CH 2 OH.
　得られた白色固体をメタノール１Ｌから再結晶することにより、２０５．０ｇの下記化合物（ａ２）（白色固体）を得た。収率は７０％であった。 The obtained white solid was recrystallized from 1 L of methanol to obtain 205.0 g of the following compound (a2) (white solid). The yield was 70%.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　得られた化合物（ａ２）の１Ｈ－ＮＭＲの測定結果を以下に示す。 The measurement result of 1 H-NMR of the obtained compound (a2) is shown below.
　１Ｈ－ＮＭＲ（溶媒：ＣＤ３ＣＯＣＤ３）δ（ｐｐｍ）：２．７７（２Ｈ、ｍ、－ＣＨ２ＣＦ２－）、４．５７（２Ｈ、ｔ、－ＣＯＯ［ＣＨ２］ＣＨ２－）、５．４７（２Ｈ、ｓ、－ＮＨ２）、６．６９（２Ｈ、ｄ、Ｐｈ）、７．７６（２Ｈ、ｄ、Ｐｈ）。 1 H-NMR (solvent: CD 3 COCD 3 ) δ (ppm): 2.77 (2H, m, —CH 2 CF 2 —), 4.57 (2H, t, —COO [CH 2 ] CH 2 — ), 5.47 (2H, s, —NH 2 ), 6.69 (2H, d, Ph), 7.76 (2H, d, Ph).
　＜ＦＴ－ＩＲ測定＞
　反応溶液の１滴をＫＢｒ窓材にたらしてはさみ、透過型ＦＴ－ＩＲ測定を行った。イソシアネート基に由来する２２８０ｃｍ－１付近のピークが完全に消失するか、またはピークがほぼ消失し、さらに２４時間反応を続けてもピークに変化が見られなくなった時点で反応を終了した。 <FT-IR measurement>
One drop of the reaction solution was put on a KBr window material and sandwiched, and transmission FT-IR measurement was performed. The reaction was terminated when the peak in the vicinity of 2280 cm −1 derived from the isocyanate group disappeared completely or almost disappeared and no further change was observed in the peak even if the reaction was continued for 24 hours.
　＜１Ｈ－ＮＭＲ測定＞
　反応後の溶液の１Ｈ－ＮＭＲ測定を行うことにより、含フッ素化合物（ａ１）（実施例１～４）、含フッ素化合物（ａ２）（実施例５～６）およびＣ６Ｆ１３Ｃ２Ｈ４ＯＨ（比較例１～２）の反応転化率を算出した。すなわち、原料の化学シフトに対して、イソシアネートと反応した後の化学シフトは主に低磁場側に現れるため、それらのシグナルの積分強度比から転化率を求めた。 <1 H-NMR measurement>
By performing 1 H-NMR measurement of the solution after the reaction, the fluorine-containing compound (a1) (Examples 1 to 4), the fluorine-containing compound (a2) (Examples 5 to 6) and C 6 F 13 C 2 H The reaction conversion rate of 4 OH (Comparative Examples 1 and 2) was calculated. That is, since the chemical shift after reacting with isocyanate appears mainly on the low magnetic field side with respect to the chemical shift of the raw material, the conversion rate was obtained from the integrated intensity ratio of these signals.
　例えば、実施例１において、化合物（ａ１）の芳香環由来の化学シフト（ＣＤＣｌ３中）および積分強度相対値は、６．９ｐｐｍ（積分強度相対値：２）および７．９ｐｐｍ（２）であり、イソシアネートと反応し、ウレタン結合を形成した反応性生物由来の化学シフトおよび積分強度相対値は、７．２ｐｐｍ（９８）および８．０ｐｐｍ（９８）であり、転化率は９８％と求められる。 For example, in Example 1, the chemical shift (in CDCl 3 ) and the integrated intensity relative value derived from the aromatic ring of the compound (a1) are 6.9 ppm (integrated intensity relative value: 2) and 7.9 ppm (2). The chemical shift and the integrated intensity relative value derived from the reactive organism that reacted with isocyanate and formed a urethane bond were 7.2 ppm (98) and 8.0 ppm (98), and the conversion rate was determined to be 98%.
　［実施例１］
  撹拌機を備えた１００ｍＬのガラス製反応器に、デスモジュールＮ－３２００（住化バイエルウレタン社製、ＨＤＩビウレット変性体、イソシアネート基含有量：２２．７質量％）の２．７７ｇ、化合物（ａ１）の７．２３ｇ、触媒としてトリエチルアミンの０．０７６ｇ、およびＭＩＢＫの４０．０ｇを入れ、室温下４８時間撹拌し、反応生成物である含フッ素ウレタン化合物を含有する反応溶液を得た。反応終了後の反応溶液のＦＴ－ＩＲでイソシアネート基のピークが消失していた。また、１Ｈ－ＮＭＲによる化合物（ａ１）の転化率は９８％であった。 [Example 1]
To a 100 mL glass reactor equipped with a stirrer, 2.77 g of Desmodur N-3200 (manufactured by Sumika Bayer Urethane Co., Ltd., modified HDI biuret, isocyanate group content: 22.7 mass%), compound (a1 ), 0.076 g of triethylamine as a catalyst, and 40.0 g of MIBK were added and stirred at room temperature for 48 hours to obtain a reaction solution containing a fluorine-containing urethane compound as a reaction product. The peak of the isocyanate group disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of compound (a1) by 1 H-NMR was 98%.
　［比較例１］
　撹拌機を備えた１００ｍＬのガラス製反応器に、デスモジュールＮ－３２００の３．３７ｇ、Ｃ６Ｆ１３Ｃ２Ｈ４ＯＨの６．６３ｇ、触媒としてジブチルすずジラウレートの０．００１３ｇ、およびＭＩＢＫの４０．０ｇを入れ、８０℃に加温して３時間撹拌し、反応生成物である含フッ素ウレタン化合物を含有する反応溶液を得た。反応終了後の反応溶液のＦＴ－ＩＲでイソシアネート基のピークが消失していた。また、１Ｈ－ＮＭＲによるＣ６Ｆ１３Ｃ２Ｈ４ＯＨの転化率は９９％であった。 [Comparative Example 1]
A 100 mL glass reactor equipped with a stirrer was charged with 3.37 g of Desmodur N-3200, 6.63 g of C 6 F 13 C 2 H 4 OH, 0.0013 g of dibutyltin dilaurate as a catalyst, and MIBK 40.0 g was added, heated to 80 ° C. and stirred for 3 hours to obtain a reaction solution containing a fluorine-containing urethane compound as a reaction product. The peak of the isocyanate group disappeared by FT-IR of the reaction solution after completion of the reaction. Further, the conversion of C 6 F 13 C 2 H 4 OH by 1 H-NMR was 99%.
　［実施例２］
　撹拌機を備えた１００ｍＬのガラス製反応器に、デュラネートＴＨＡ－１００（旭化成ケミカルズ社製、ＨＤＩヌレート変性体、イソシアネート基含有量：２１．２質量％）の２．９０ｇ、化合物（ａ１）の７．１０ｇ、触媒としてトリエチルアミンの０．０７４ｇ、およびＭＩＢＫの４０．０ｇを入れ、室温下４８時間撹拌し、反応生成物である含フッ素ウレタン化合物を含有する反応溶液を得た。反応終了後の反応溶液のＦＴ－ＩＲでイソシアネート基のピークがほぼ消失していた。また、１Ｈ－ＮＭＲによる化合物（ａ１）の転化率は９５％であった。 [Example 2]
To a 100 mL glass reactor equipped with a stirrer, 2.90 g of Duranate THA-100 (manufactured by Asahi Kasei Chemicals, modified HDI nurate, isocyanate group content: 21.2% by mass), 7 of compound (a1) .10 g, 0.074 g of triethylamine as a catalyst, and 40.0 g of MIBK were added and stirred at room temperature for 48 hours to obtain a reaction solution containing a fluorine-containing urethane compound as a reaction product. The isocyanate group peak almost disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of the compound (a1) by 1 H-NMR was 95%.
　［比較例２］
　撹拌機を備えた１００ｍＬのガラス製反応器に、デュラネートＴＨＡ－１００の３．５２ｇ、Ｃ６Ｆ１３Ｃ２Ｈ４ＯＨの６．４８ｇ、触媒としてジブチルすずジラウレートの０．００１２ｇ、およびＭＩＢＫの４０．０ｇを入れ、８０℃に加温して３時間撹拌し、反応生成物である含フッ素ウレタン化合物を含有する反応溶液を得た。反応終了後の反応溶液のＦＴ－ＩＲでイソシアネート基のピークが消失していた。また、１Ｈ－ＮＭＲによるＣ６Ｆ１３Ｃ２Ｈ４ＯＨの転化率は９９％であった。 [Comparative Example 2]
A 100 mL glass reactor equipped with a stirrer was charged with 3.52 g of Duranate THA-100, 6.48 g of C 6 F 13 C 2 H 4 OH, 0.0012 g of dibutyltin dilaurate as a catalyst, and 40 MIBK. 0.0 g was added, heated to 80 ° C. and stirred for 3 hours to obtain a reaction solution containing a fluorine-containing urethane compound as a reaction product. The peak of the isocyanate group disappeared by FT-IR of the reaction solution after completion of the reaction. Further, the conversion of C 6 F 13 C 2 H 4 OH by 1 H-NMR was 99%.
　［実施例３］
　撹拌機を備えた１００ｍＬのガラス製反応器に、コスモネートＭ－２００（三井化学ポリウレタン社製、ポリメリックＭＤＩ、イソシアネート基含有量：３１．５質量％）の２．１６ｇ、化合物（ａ１）の７．８４ｇ、触媒としてトリエチルアミンの０．０８２ｇ、およびＭＩＢＫの４０．０ｇを入れ、室温下１００時間撹拌し、反応生成物である含フッ素ウレタン化合物を含有する反応溶液を得た。反応終了後の反応溶液のＦＴ－ＩＲでイソシアネート基のピークがほぼ消失していた。また、１Ｈ－ＮＭＲによる化合物（ａ１）の転化率は９０％であった。 [Example 3]
To a 100 mL glass reactor equipped with a stirrer, 2.16 g of Cosmonate M-200 (manufactured by Mitsui Chemicals Polyurethanes, Polymeric MDI, isocyanate group content: 31.5 mass%), 7 of compound (a1) .84 g, 0.082 g of triethylamine as a catalyst, and 40.0 g of MIBK were added and stirred at room temperature for 100 hours to obtain a reaction solution containing a fluorine-containing urethane compound as a reaction product. The isocyanate group peak almost disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of the compound (a1) by 1 H-NMR was 90%.
　［実施例４］
　撹拌機を備えた１００ｍＬのガラス製反応器に、ＴＤＩ（東京化成工業社製、イソシアネート基含有量：４８．３質量％）の１．５２ｇ、化合物（ａ１）の８．４８ｇ、触媒としてトリエチルアミンの０．０８９ｇ、およびＭＩＢＫの４０．０ｇを入れ、室温下１００時間撹拌し、反応生成物である含フッ素ウレタン化合物を含有する反応溶液を得た。反応終了後の反応溶液のＦＴ－ＩＲでイソシアネート基のピークがほぼ消失していた。また、１Ｈ－ＮＭＲによる化合物（ａ１）の転化率は９２％であった。 [Example 4]
In a 100 mL glass reactor equipped with a stirrer, 1.52 g of TDI (manufactured by Tokyo Chemical Industry Co., Ltd., isocyanate group content: 48.3 mass%), 8.48 g of compound (a1), triethylamine as a catalyst 0.089 g and 40.0 g of MIBK were added and stirred at room temperature for 100 hours to obtain a reaction solution containing a fluorine-containing urethane compound as a reaction product. The isocyanate group peak almost disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of compound (a1) by 1 H-NMR was 92%.
　［実施例５］
　撹拌機を備えた１００ｍＬのガラス製反応器に、ＴＤＩの１．５３ｇ、化合物（ａ２）の８．４７ｇ、およびＭＩＢＫの４０．０ｇを入れ、８０℃に加温して１００時間撹拌し、反応生成物である含フッ素ウレア化合物を含有する反応溶液を得た。反応終了後の反応溶液のＦＴ－ＩＲでイソシアネート基のピークがほぼ消失していた。また、１Ｈ－ＮＭＲによる化合物（ａ２）の転化率は８８％であった。 [Example 5]
A 100 mL glass reactor equipped with a stirrer was charged with 1.53 g of TDI, 8.47 g of compound (a2), and 40.0 g of MIBK, heated to 80 ° C., stirred for 100 hours, and reacted. A reaction solution containing a fluorine-containing urea compound as a product was obtained. The isocyanate group peak almost disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of compound (a2) by 1 H-NMR was 88%.
　［実施例６］
　撹拌機を備えた１００ｍＬのガラス製反応器に、ＭＤＩ（東京化成工業社製、イソシアネート基含有量：３３．６質量％）の２．０６ｇ、化合物（ａ２）の７．９４ｇ、およびＭＩＢＫの４０．０ｇを入れ、８０℃に加温して１００時間撹拌し、反応生成物である含フッ素ウレア化合物を含有する反応溶液を得た。反応終了後の反応溶液のＦＴ－ＩＲでイソシアネート基のピークがほぼ消失していた。また、１Ｈ－ＮＭＲによる化合物（ａ２）の転化率は８５％であった。 [Example 6]
In a 100 mL glass reactor equipped with a stirrer, 2.06 g of MDI (manufactured by Tokyo Chemical Industry Co., Ltd., isocyanate group content: 33.6% by mass), 7.94 g of compound (a2), and 40 of MIBK 0.0 g was added, and the mixture was heated to 80 ° C. and stirred for 100 hours to obtain a reaction solution containing a fluorine-containing urea compound as a reaction product. The isocyanate group peak almost disappeared by FT-IR of the reaction solution after completion of the reaction. The conversion rate of the compound (a2) by 1 H-NMR was 85%.
　＜評価１（接触角）＞
　上記実施例１～６、比較例１～２で得られた反応溶液のそれぞれについて、下記の方法にて試験板を作製して、撥水撥油性を評価した。 <Evaluation 1 (Contact angle)>
For each of the reaction solutions obtained in Examples 1 to 6 and Comparative Examples 1 and 2, test plates were prepared by the following method to evaluate water and oil repellency.
　［試験板の作製］
　得られた反応溶液を固形分濃度が１．０質量％となるようにアセトン（実施例１～４および比較例１～２）またはＤＭＦ（実施例５～６）にて希釈し、処理液とした。次いで、以下に示す方法に従って前記各処理液を用いて、ガラス板上に皮膜を形成させ、該皮膜の撥水撥油性評価を行った。評価結果を表１に示す。 [Preparation of test plate]
The obtained reaction solution was diluted with acetone (Examples 1 to 4 and Comparative Examples 1 to 2) or DMF (Examples 5 to 6) so that the solid content concentration was 1.0% by mass. did. Next, a film was formed on the glass plate using each of the treatment liquids according to the following method, and the water and oil repellency of the film was evaluated. The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　［接触角測定］
　洗浄済みのガラス板を基材として用い、その上に上記で得られた処理液をスピンコート法にて、１０００ｒｐｍの条件で１０秒間塗布した。この後、１２０℃にて６０分間加熱処理して皮膜を形成し、試験板を得た。上記処理液すべてについて、これを用いて皮膜形成させた試験板を作製し、得られた各試験板を用いて、該皮膜上の水およびｎ－ヘキサデカンの接触角を測定することにより、上記実施例、比較例で作製した撥水撥油剤を含む処理液から得られる皮膜の撥水撥油性を評価した。なお、接触角の測定は、協和界面科学社製ＣＡ－Ｘを用いて行った。 [Contact angle measurement]
A washed glass plate was used as a substrate, and the treatment liquid obtained above was applied thereon by spin coating for 10 seconds under the condition of 1000 rpm. Thereafter, a film was formed by heat treatment at 120 ° C. for 60 minutes to obtain a test plate. Using all of the above treatment solutions, a test plate formed with a film was prepared, and each test plate obtained was used to measure the contact angles of water and n-hexadecane on the coating. The water and oil repellency of the film obtained from the treatment liquid containing the water and oil repellent prepared in Examples and Comparative Examples was evaluated. The contact angle was measured using CA-X manufactured by Kyowa Interface Science Co., Ltd.
　表中＊を付した接触角の値は測定中に皮膜上の液滴が濡れ広がったために正確な値ではなく、また、液滴が濡れ広がったことは撥水性が不十分と言い換えることができる。 The contact angle value marked with * in the table is not an accurate value because the droplet on the film wets and spreads during the measurement, and it can be said that the water repellency is insufficient when the droplet spreads wet. .
　これらの結果から本発明の撥水撥油剤を含有する処理液（撥水剤組成物）は、本発明の撥水撥油剤の構成成分のいずれかを含まない比較例の撥水撥油剤を含有する処理液（撥水撥油剤組成物）に比べ、高い撥水撥油性を有する皮膜が作製可能なことがわかる。また、本発明の撥水撥油剤を含有する処理液（撥水撥油剤組成物）を用いれば、物品に十分な撥水撥油性を付与することが可能であり、環境負荷も低い。 From these results, the treatment liquid (water repellent composition) containing the water / oil repellent of the present invention contains the water / oil repellent of the comparative example which does not contain any of the components of the water / oil repellent of the present invention. It can be seen that a film having higher water / oil repellency can be produced than the treatment liquid (water / oil repellent composition). Moreover, if the processing liquid (water / oil repellent composition) containing the water / oil repellent of the present invention is used, sufficient water / oil repellency can be imparted to the article, and the environmental load is low.
　＜評価２＞
　上記実施例１～６、比較例１～２で得られた反応溶液のそれぞれについて、下記の方法にて試験布を作製して、撥水性および撥油性を評価した。 <Evaluation 2>
For each of the reaction solutions obtained in Examples 1 to 6 and Comparative Examples 1 and 2, test cloths were prepared by the following method to evaluate water repellency and oil repellency.
　［試験布の作製］
　得られた反応溶液を固形分濃度が０．６ｇ／Ｌとなるようにアセトン（実施例１～４および比較例１～２）またはＤＭＦ（実施例５～６）にて希釈し、試験液とした。これらの試験液にポリエステル布を浸漬し、ウェットピックアップが１００質量％となるように絞った。これを、常温で２４時間乾燥し、さらに１７０℃で６０秒間乾燥したものを試験布とした。 [Preparation of test cloth]
The obtained reaction solution was diluted with acetone (Examples 1 to 4 and Comparative Examples 1 to 2) or DMF (Examples 5 to 6) so that the solid content concentration was 0.6 g / L. did. A polyester cloth was soaked in these test solutions, and the wet pick-up was squeezed to 100% by mass. This was dried at room temperature for 24 hours and further dried at 170 ° C. for 60 seconds to obtain a test cloth.
　［撥水性の評価］
　試験布の撥水性の評価はＪＩＳ－Ｌ１０９２のスプレー試験により行い、表２に示す撥水性等級で表した。撥水性等級に＋（－）を記したものは、それぞれの性質がわずかに良い（悪い）ことを示す。評価結果を表１に示す。 [Evaluation of water repellency]
The water repellency of the test cloth was evaluated by the spray test of JIS-L1092, and the water repellency rating shown in Table 2 was used. Those marked with + (−) in the water repellency grade indicate that the respective properties are slightly good (bad). The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　［撥油性の評価］
　ＡＡＴＣＣ－ＴＭ１１８－１９６６の試験法に従い、表３に示す試験溶液を、上記で作製した各試験布Ａ上の２ヶ所にそれぞれ数滴（径約４ｍｍ）置き、３０秒後の浸漬状態により表３に示す撥油性等級（ナンバ）で表した。なお、撥油性等級に＋（－）を記したものは、それぞれの評価がわずかに良い（悪い）ことを示す。評価結果を表１に示す。 [Evaluation of oil repellency]
In accordance with the test method of AATCC-TM118-1966, a few drops (about 4 mm in diameter) of the test solutions shown in Table 3 were placed in two places on each test cloth A prepared above, and the test solution was immersed in 30 seconds. It was represented by the oil repellency rating (number). Note that an oil repellency rating of + (−) indicates that each evaluation is slightly good (bad). The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　これらの結果から本発明の撥水撥油剤を含有する撥水撥油剤組成物を用いて物品を処理すれば、本発明の撥水撥油剤の構成成分のいずれかを含まない比較例の撥水撥油剤を含有する撥水撥油剤組成物に比べ、高い撥水撥油性を付与可能なことがわかる。 From these results, if the article is treated with the water / oil repellent composition containing the water / oil repellent of the present invention, the water repellency of the comparative example which does not contain any of the components of the water / oil repellent of the present invention. It can be seen that high water and oil repellency can be imparted compared to a water and oil repellent composition containing an oil repellent.
　本発明の撥水撥油剤または撥水撥油剤組成物は、繊維製品（衣料物品（スポーツウェア、コート、ブルゾン、作業用衣料、ユニフォーム等。）、かばん、カーペット、カーテン、壁紙、車輌の内装品、産業資材等。）、不織布、皮革製品、石材、コンクリート系建築材料、等の撥水撥油剤として有用である。また、濾過材料用コーティング剤、表面保護剤として有用である。さらに、ポリプロピレン、ナイロン、ポリエステル等と混合して成形、繊維化することにより撥水撥油性を付与する用途にも有用である。
　なお、２０１０年６月４日に出願された日本特許出願２０１０－１２９０１２号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The water / oil repellent or water / oil repellent composition of the present invention is used for textile products (clothing articles (sportswear, coats, blousons, work clothes, uniforms, etc.), bags, carpets, curtains, wallpaper, and vehicle interiors. , Industrial materials, etc.), non-woven fabrics, leather products, stone materials, concrete building materials, and the like. Moreover, it is useful as a coating agent for filter materials and a surface protective agent. Furthermore, it is also useful for applications in which water and oil repellency is imparted by mixing and molding with fiber such as polypropylene, nylon and polyester.
It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2010-129002 filed on June 4, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (8)

  1. 　下記含フッ素化合物（ａ）とポリイソシアネート化合物（ｂ）との反応生成物とを含有することを特徴とする撥水撥油剤。
      含フッ素化合物（ａ）：Ｒｆ－Ｘ－Ｐｈ－Ｙ－Ｚ
    Ｒｆは炭素数１～６のポリフルオロアルキル基を、Ｘは単結合、炭素数１～４のアルキレン基、（ＣＨ２）ｍＯ（ＣＨ２）ｎ（ｍおよびｎは互いに独立して０～４の整数）、または（ＣＨ２）ｐＯＣＯ（ｐは１～４の整数）を、Ｐｈはフェニレン基を、Ｙは単結合、炭素数１～４のアルキレン基、または（ＣＨ２）ｑＯ（ＣＨ２）ｒ（ｑは０～４の整数、ｒは１～４の整数）を、ＺはＯＨまたはＮＨＲ（Ｒは水素原子または炭素数１～６のアルキル基）をそれぞれ表す。     A water / oil repellent comprising the following fluorine-containing compound (a) and a reaction product of a polyisocyanate compound (b).
    Fluorine-containing compound (a): R f —X—Ph—YZ
    R f is a polyfluoroalkyl group having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 4 carbon atoms, (CH 2 ) m O (CH 2 ) n (m and n are each independently 0 Or an integer of 1 to 4), or (CH 2 ) p OCO (p is an integer of 1 to 4), Ph is a phenylene group, Y is a single bond, an alkylene group having 1 to 4 carbon atoms, or (CH 2 ) q O (CH 2 ) r (q is an integer of 0 to 4, r is an integer of 1 to 4), and Z is OH or NHR (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
  2. 　前記反応生成物が、イソシアネート基を有しない請求項１に記載の撥水撥油剤。 The water / oil repellent according to claim 1, wherein the reaction product does not have an isocyanate group.
  3. 　前記含フッ素化合物（ａ）のＲｆが炭素数４～６のパーフルオロアルキル基である、請求項１または２に記載の撥水撥油剤。 The water / oil repellent according to claim 1 or 2, wherein R f of the fluorine-containing compound (a) is a perfluoroalkyl group having 4 to 6 carbon atoms.
  4. 　前記含フッ素化合物（ａ）が下式（ａ１）または（ａ２）で表される含フッ素化合物である、請求項１～３のいずれかに記載の撥水撥油剤。
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
         The water / oil repellent according to any one of claims 1 to 3, wherein the fluorine-containing compound (a) is a fluorine-containing compound represented by the following formula (a1) or (a2).
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
  5. 　前記ポリイソシアネート化合物（ｂ）が、ヘキサメチレンジイソシアネートまたはその変性体である、請求項１～４のいずれかに記載の撥水撥油剤。 The water / oil repellent according to any one of claims 1 to 4, wherein the polyisocyanate compound (b) is hexamethylene diisocyanate or a modified product thereof.
  6. 　さらに、ポリイソシアネート（ｂ）とイソシアネート基と反応性のある活性水素基を有する化合物（ｃ）との反応生成物、またはポリイソシアネート（ｂ）と、含フッ素化合物（ａ）およびイソシアネート基と反応性のある活性水素基を有する化合物（ｃ）との反応生成物を含有する請求項１～５のいずれかに記載の撥水撥油剤。 Furthermore, the reaction product of the polyisocyanate (b) and the compound (c) having an active hydrogen group reactive with the isocyanate group, or the polyisocyanate (b), the fluorine-containing compound (a) and the reactivity with the isocyanate group The water / oil repellent according to any one of claims 1 to 5, comprising a reaction product with a compound (c) having an active hydrogen group.
  7. 　請求項１～６のいずれかに記載の撥水撥油剤と溶媒を含有する撥水撥油剤組成物。 A water / oil repellent composition comprising the water / oil repellent according to any one of claims 1 to 6 and a solvent.
  8. 　固形分濃度が、０．０５～１０質量％である請求項７に記載の撥水撥油剤組成物。 The water / oil repellent composition according to claim 7, wherein the solid content concentration is 0.05 to 10% by mass.
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